Rinse aid surface coating compositions for modifying dishware surfaces

ABSTRACT

Rinse aid materials for coating, coating compositions, methods and articles of manufacture for use in automatic dishwashing appliances comprising a nanoparticle system or employing the same to impart surface modifying benefits for all types of dishware surfaces are disclosed. In some embodiments, dispersement of nanoparticles in a suitable carrier medium allows for the creation of rinse aid surface coating compositions, methods and articles of manufacture that create multi-use benefits to modified dishware surfaces. These surface modifications can produce long lasting or semi-permanent multi-use benefits that include at least one of the following improved surface properties: wetting and sheeting, uniform drying, anti-spotting, anti-staining, anti-filming, self cleaning, and durability benefits, relative to dishware surfaces unmodified with such nanoparticle systems. In some embodiments, actively curing the rinse aid surface coating composition on the dishware surfaces, including, but not limited to by radiative heating the air surrounding the dishware surface with the coating thereon can be used to increase the durability of the dishware surface coating.

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of the filing dates of PCTapplication Ser. No. US00/16349, filed Jun. 14, 2000, U.S. Provisionalpatent application Serial No. 60/265,059, filed Jan. 30, 2001 (8407P),and a continuation-in-part of U.S. patent application Ser. No.09/828,014, filed Apr. 6, 2001 (8495), U.S. patent application Ser. No.09/876,363, filed Jun. 7, 2001 (8407M), U.S. patent application Ser. No.09/950,757, filed Sep. 11, 2001 (8711) and U.S. patent application Ser.No. 09/972,090, filed Oct. 5, 2001 (8711R).

FIELD OF THE INVENTION

[0002] The present invention relates to rinse aid surface coatings,compositions, methods and articles of manufacture comprising ananoparticle system or employing the same to impart surface modifyingbenefits for all types of dishware surfaces in automatic dishwashingapplications.

[0003] The use of non-photoactive nanoparticles allows for the creationof rinse aid surface coatings, compositions, methods and articles ofmanufacture that create multi-use benefits to modified dishwaresurfaces. These surface modifications can produce durable, protective,long lasting or semi-permanent multi-use benefits that include at leastone of the following improved surface properties: wetting and sheeting,uniform drying, anti-spotting, anti-staining, anti-filming, selfcleaning, and durability, relative to dishware surfaces unmodified withsuch nanoparticle systems.

BACKGROUND OF THE INVENTION

[0004] There have been many problems associated with developing rinseaid surface coatings for dishware that provide a beneficial layer withthe desirable properties and which minimize the disadvantages, such as alimit to single use protection, insufficient coverage, roughness and/orflaking of coating during use, or in contrast, the inability to removeonce applied (when a more temporary coating is desired) and a limit onsurfaces that can be modified.

[0005] Current approaches to solving the coating problem includes theuse of non-dispersive, film-forming polymer coatings andclay-containing, non-dispersive, film-forming polymer coatings. However,the substantivity of the non-dispersive, film-forming polymers (e.g.alkoxylated silicones, poly(N-vinyl-2-pyrrolidones,poly(N-vinyl-imidazoles, diblock copolymers of poly(ethylene oxide) andpoly(lactide)) is poor such that its wetting/sheeting effect isshort-lived, with spotting/residue negatives returning within 1-2 rinsecycles. Elevating the levels of non-dispersive polymers is not thesolution to this problem. This is especially evident on dishware whereelevated levels of polymers result in unacceptable residue or filmproblems. In the case of clay-containing, non-dispersive, film-formningpolymer coatings, the nanoparticles are rheology agents for theformulations and do not themselves impart the benefit disclosed.

[0006] It is apparent that there is a continuing need to improve thevarious properties of all dishware surfaces in automatic dishwashers,including but not limited to plastics, metals, glass, wood and stonesurfaces, via a dispersive coating composition and method of use whichwould result in dishware surfaces having one or more of the followinghighly desirable modified surface properties such as improved wettingand sheeting, uniform drying, anti-spotting, anti-staining,anti-filming, self cleaning, and durability. There is also a continuingneed that these modified surface benefits be made the more responsive toconsumer applications.

[0007] Additional background patents and patent publications, some ofwhich disclose various uses of nanoparticles, include: U.S. Pat. Nos.4,591,499 and 4,597,886; JP 04-353438; U.S. Pat. No. 5,429,867; JP96053558; GB 2 303 373; U.S. Pat. No. 5,853,809; PCT WO 99/00457; WO00/000554 Al; WO 01/27236; and WO 01/32820.

SUMMARY OF THE INVENTION

[0008] The present invention relates to rinse aid materials, coatings,compositions, methods, and articles of manufacture that provide someimportant dishware surface multi-use benefits that can be made durable,protective, long lasting or semi-permanent in the automatic dishwasherenvironment. These multi-use benefits include at least one of thefollowing: improved wetting and sheeting, uniform drying, anti-spotting,anti-staining, anti-filming, self cleaning, and durability relative tosurfaces that are not treated with the rinse aid materials, coatings, orcoating compositions. The rinse aid surface coating composition of thepresent invention can be used in the automatic dishwashing cycle inconjunction with a general detergent or actually as a rinse aid in therinsing or pre-drying cycle. The following are some non-limitingembodiments of the present invention.

[0009] In one embodiment of the present invention there is provided arinse aid material for coating the dishware surfaces. As used herein,the term “coating” includes coatings that completely cover a surface, orportion thereof, as well as coatings that may only partially cover asurface, such as those coatings that after drying leave gaps in coverageon a surface. The later category of coatings may include, but is notlimited to a network of covered and uncovered portions (e.g.,non-continuous covered regions of the surface). When the coatingsdescribed herein are described as being applied to a surface, it isunderstood that the coatings need not be applied to, or that they coverthe entire surface. For instance, the coatings will be considered asbeing applied to a surface even if they are only applied to modify aportion of the surface.

[0010] As used herein, the term “coating” includes coatings thatcompletely cover a surface, or portion thereof, as well as coatings thatmay only partially cover a surface, such as those coatings that afterdrying leave gaps in coverage on a surface. The later category ofcoatings may include, but is not limited to a network of covered anduncovered portions (e.g., non-continuous covered regions of thesurface). When the coatings described herein are described as beingapplied to a surface, it is understood that the coatings need not beapplied to, or that they cover the entire surface. For instance, thecoatings will be considered as being applied to a surface even if theyare only applied to modify a portion of the surface. The rinse aidmaterial for coating the dishware surfaces can comprise a plurality ofnon-photoactive nanoparticles, or it can comprise a singlenon-photoactive nanoparticle surface coating composition. Such a coatingcomposition may comprise: (a) an effective amount of non-photoactivenanoparticles; (b) a dispersant polymer; (c) optionally a surfactant;(d) optionally having associated to said nanoparticle surface a quantityof one or more functionalized surface molecules exhibiting propertiesselected from the group consisting of hydrophilic, hydrophobic andmixtures thereof; (e) optionally one or more adjunct ingredients; and(f) optionally a suitable carrier medium.

[0011] In another embodiment of the present invention, there is provideda method of applying a substantially clear coating to a dishware surfaceduring the rinse cycle of an automatic dishwashing appliance comprising:applying a material comprising an effective amount of non-photoactivenanoparticles to the dishware surface; and, actively curing the materialto form a coating on the dishware surface.

[0012] In another embodiment of the present invention, there may beprovided a rinse aid surface coating composition for coating thedishware surfaces comprising (a) an effective amount of non-photoactivenanoparticles; (b) a dispersant polymer selected from the groupconsisting of polyacrylic acid, poly (acrylic/allyl alcohol), poly(acrylic/maleic), polycarboxylic acids, sodium tripolyphosphate,pyrophosphate, and mixtures thereof; (c) optionally a surfactant; (d)optionally having associated to said nanoparticle surface a quantity ofone or more functionalized surface molecules exhibiting propertiesselected from the group consisting of hydrophilic, hydrophobic andmixtures thereof; (e) optionally one or more adjunct ingredients; and(f) optionally a suitable carrier medium.

[0013] In another embodiment of the present invention, there may beprovided a rinse aid surface coating composition for coating thedishware surfaces comprising (a) an effective amount of non-photoactivenanoparticles wherein the photoactive nanoparticles are selected fromthe group consisting of Lucentite SWN™, LAPONITE B™, LAPONITE S™,LAPONITE XLS™, LAPONITE RD™ and LAPONITE RDS™, and mixtures thereof; (b)a dispersant polymer; (c) optionally a surfactant; (d) optionally havingassociated to said nanoparticle surface a quantity of one or morefunctionalized surface molecules exhibiting properties selected from thegroup consisting of hydrophilic, hydrophobic and mixtures thereof; (e)optionally one or more adjunct ingredients; and (f) optionally asuitable carrier medium.

[0014] One embodiment of this invention uses LAPONITE XLS™ having thefollowing characteristics: analysis (dry basis) SiO₂ 59.8%, MgO 27.2%,Na₂O 4.4%, Li₂O 0.8%, structural H₂O 7.8%, with the addition oftetrasodium pyrophosphate (6%); specific gravity 2.53; bulk density 1.0.

[0015] In another embodiment of the present invention, there may beprovided a rinse aid surface coating composition for coating thedishware surfaces comprising (a) an effective amount of non-photoactivenanoparticles wherein the photoactive nanoparticles are selected fromthe group consisting of LAPONITE RD™ and LAPONITE B™, and mixturesthereof; (b) a dispersant polymer selected from the group consisting ofpolyacrylic acid, poly (acrylic/allyl alcohol), poly (acrylic/maleic),polycarboxylic acids, sodium tripolyphosphate, pyrophosphate, andmixtures thereof; (c) optionally a surfactant; (d) optionally havingassociated to said nanoparticle surface a quantity of one or morefunctionalized surface molecules exhibiting properties selected from thegroup consisting of hydrophilic, hydrophobic and mixtures thereof; (e)optionally one or more adjunct ingredients; and (f) optionally asuitable carrier medium.

[0016] In another embodiment of the present invention there may beprovided a method of using a rinse aid surface coating composition by(a) mixing said nanoparticles in suitable carrier medium to form saidsurface coating composition; (b) mixing said nanoparticles dispersed insuitable carrier medium with a dispersant polymer to inhibit gelformation; (c) optionally mixing said nanoparticles dispersed insuitable carrier medium with a dispersant polymer and adjunctingredients to form said surface coating composition; (d) optionallymixing said nanoparticles dispersed in suitable carrier medium with adispersant polymer and a surfactant to form said surface coatingcomposition; (e) optionally mixing said nanoparticles dispersed insuitable carrier medium with a dispersant polymer and a pH-adjustingagent to form said surface coating composition; (f) optionally mixingsaid nanoparticles dispersed in suitable carrier medium with adispersant polymer, adjunct ingredients and surfactant to form saidsurface coating composition; (g) optionally mixing said nanoparticlesdispersed in suitable carrier medium with a dispersant, a surfactant, apH-adjusting agent and adjunct ingredients to form said surface coatingcomposition; (h) applying said surface coating composition to a dishwaresurface; (i) allowing said surface coating composition to dry, or dryingthe rinse aid surface coating composition; and (j) optionally repeatingany of steps (a) through (i) as needed.

[0017] The drying step can comprise air drying in ambient conditions, orit can comprise actively drying the rinse aid surface coatingcomposition by utilizing any technology known for accelerating thedrying process (such as, in the drying cycle of an automatic dishwashingappliance). It has been found the heat drying the rinse aid surfacecoating composition can greatly increase the durability of the dishwaresurface coating.

[0018] In another embodiment of the present invention there may beprovided an article of manufacture comprising an applicator, such as anautomatic dishwashing appliance spray dispenser, a spray dispenser, animmersion container, a hose spray dispenser attachment, a fabric or aporous article, such as a sponge; further comprising (a) a dishwarecoating composition, wherein said surface coating composition may be inthe physical form selected from the group consisting of liquid, liquidconcentrate, gel, powder, tablet, granule and mixtures thereof; (b)optionally a source of water or deionized water; and (c) optionally aset of instructions in association with said spray dispenser comprisingan instruction to dispense said surface coating composition from saidspray dispenser onto said dishware surface.

[0019] In another embodiment of the present invention there may beprovided a treated dishware surface coated with the rinse aid surfacecoating composition. Substrates treated with the benefit agent materialsof the present invention exhibit a greater improvement in wetting andsheeting, uniform drying, anti-spotting, anti-staining, staining,anti-filming, self cleaning, and durability than substrates treatedwithout such benefit agent materials.

[0020] In another embodiment of the invention there may be provided atreated dishware surface coated with a rinse aid surface coatingcomposition, where the rinse aid surface coating composition may bestrippable. Substrates treated with the benefit agent materials of thepresent invention exhibit a greater improvement in wetting and sheeting,uniform drying, anti-spotting, anti-staining, staining, anti-filming,self cleaning, and durability after at least one effective nanoparticlelayer has been stripped than substrates treated without such benefitagent materials.

[0021] Numerous other embodiments are also possible. These elements ofthe embodiments described herein can also be combined in other ways, orwith other elements to create still further embodiments.

[0022] All percentages, ratios and proportions herein are on a weightbasis based on a neat product unless otherwise indicated. All documentscited herein are hereby incorporated by reference.

BRIEF DESCRIPTION OF THE DRAWINGS

[0023] While the specification concludes with claims particularlypointing out and distinctly claiming the subject matter which may beregarded as forming the present invention, it is believed that theinvention will better understood from the following description taken inconjunction with the accompanying drawings, in which:

[0024]FIG. 1 is a schematic side view of a dishware surface with severallayers of nanoparticles that form a rinse aid surface coating thereon,and stain on a portion of the nanoparticle coating.

[0025]FIG. 2 is a schematic side view similar to FIG. 1, only showinghow the removal of the top layer of nanoparticles may remove the staindeposited on the coating.

[0026]FIG. 3 is a schematic side view similar to FIGS. 1 and 2 showing afurther step in the removal process.

[0027]FIGS. 4a-d are photographs taken of a non-limiting example of thedrying benefit observed on treated plastic dishware in comparison tonon-treated dishware surfaces. FIG. 4a is the sample on the top leftside and represents a sample treated with LAPONITE RD™. FIG. 4b is thesample on the top right side and represents a sample treated withLAPONITE B™. FIG. 4c is the sample on the bottom left and represents anuntreated sample with no rinse aid applied. FIG. 4d is the sample on thebottom right and represents a sample treated with a commercial rinseaid. The more droplets of water remaining on the dishware surface meansthe less drying benefit observed.

[0028]FIG. 5 is a photograph taken by atomic force microscopy of anon-limiting example of a nanoparticle coating which provides effectivehydrophilic modification of a surface wherein the image on the left siderepresents the topography of the treated sample using LAPONITE B™, andthe image on the right side represents the phase of the treated sampleusing LAPONITE RD™.

[0029]FIG. 6 is a photograph taken by atomic force microscopy of anon-limiting example of a nanoparticle coating which providesconsiderably less effective hydrophilic modification of a surfacewherein the image on the left side represents the topography of thetreated sample, and the image on the right side represents the phase ofthe treated sample.

DETAILED DESCRIPTION OF THE INVENTION Dishware Surfaces

[0030] There are a number of distinct dishware surface types available.Dishware can include cookware, tableware, glassware, stoneware, ceramicware, plasticware, wood ware and metal ware. Non-limiting examples ofdishware include agateware, basalt, bisque, bone china, cauliflowerware, cream ware, delft, earthenware, flambe, hard paste porcelain,ironstone, jackfield, jasper, lusterware, majolica, marbled, parian,pate-sur-pate, pearl ware, porcelain, redware, salt glaze, slipware,snowman-porcelain, soft paste porcelain, spatter ware, staffordshirefigures, stoneware, tortoiseshell, and transfer ware. Utensils can alsobe made from any of the above materials.

[0031] There are seven basic types of plastics dishware which includepolyethylene terephthalate (PET), high density polyethylene (HDPE),polyvinyl chloride (PVC), low density polyethylene (LDPE), polypropylene(PP), polystyrene (PS), polymers and mixtures thereof. These types ofplastic dishware may also be combined with other materials including,but not limited to nanoparticles, to make all sorts of composites.Manufacturers are unlimited in the number and types of articles that canbe made from plastic. Carbon and graphite fibers are high-strengthmaterials that are used as reinforcing agents in plastic composites.Examples of plastic articles include plates, bowls, bottles, jars, jugs,containers, caps, cups, trays.

[0032] Generally, only metal ware with nonferrous metal surfaces areavailable for use with this invention. These include aluminum, brass,bronze, chrome, copper and stainless steel. Examples of metal surfacesinclude (e.g. utensils, plates, cups, pans, and many more too numerousto mention).

[0033] There are three basic types of glassware—sheet, plate, and float.These basic glass types can be changed to meet modern requirements forcomfort, security, safety, and architectural needs by adding chemicalsor other optional ingredients during fabrication and processing.

[0034] There are many types of wood ware available. Articles made fromwood can include utensils, plates, cups, pans, and many more toonumerous to mention.

[0035] Ceramic ware surfaces include glazed, mosaic and quarry dishware.Examples of ceramic dishware surfaces include (e.g. utensils, plates,cups, pans, and many more too numerous to mention).

[0036] Finally, stoneware surfaces are also examples that can bemodified by the present invention to derive the desired benefits.

[0037] In certain aspects, the dishware surfaces described herein aremore rigid than a synthetic resin film having a thickness of 0.1 mm. Incertain aspects, the dishware surfaces described herein arealternatively rigid or semi-rigid (not flexible). Examples of dishwaresurfaces that are not considered to be rigid or semi-rigid would includefilms. Examples of dishware surfaces that can be considered semi-rigidare plasticware. Examples of dishware surfaces that can be consideredrigid are glassware, ceramic ware, plasticware, wood ware and metalware.

[0038] In certain aspects, the glassware and plasticware surfacesdescribed herein need not be transparent. That is, the surfaces may betranslucent or opaque.

Nanoparticle System

[0039] The nanoparticle system comprises a dishware surface modifyingagent comprising a plurality of non-photoactive nanoparticles. Thenanoparticle systems may be distinguished from colloids (small particlessuspended in solution) in that the nanoparticles are capable of forminga rinse aid surface coating or layer after the composition is applied toa dishware surface, whereas colloids are typically only thought of asbeing dispersed in another media.

[0040] The nanoparticle system can comprise materials, compositions,devices, appliances, procedures, methods, conditions, etc. serving acommon purpose of the modification of dishware surfaces to bring aboutone or more of the following: improved wetting and sheeting, uniformdrying, anti-spotting, anti-staining, anti-filming, self cleaning, anddurability.

[0041] Nanoparticles, defined as particles with diameters of about 400nm or less, are technologically significant, since they are utilized tofabricate structures, coatings, and devices that have novel and usefulproperties due to the very small dimensions of their particulateconstituents. Nanoparticles with particle sizes ranging from about 1 nmto about 400 nm can be economically produced. Particle sizedistributions of the nanoparticles in the present invention may fallanywhere within the range from about 1 nm, or less, to less than about400 nm, alternatively from about 1 nm to less than about 100 nm, andalternatively from about 1 nm to less than about 50 nm. For example, alayer synthetic silicate can have a mean particle size of about 25nanometers while its particle size distribution can generally varybetween about 10 nm to about 40 nm. Alternatively, nanoparticles canalso include crystalline or amorphous particles with a particle sizefrom about 1, or less, to about 100 nanometers, alternatively from about1 to about 50 nanometers. Nanotubes can include structures up to 1centimeter long, alternatively with a particle size from about 1, orless, to about 50 nanometers.

[0042] Inorganic nanoparticles generally exist as oxides, silicates,carbonates and hydroxides. Some layered clay minerals and inorganicmetal oxides can be examples of nanoparticles. The layered clay mineralssuitable for use in the present invention include those in thegeological classes of the smectites, the kaolins, the illites, thechlorites, the attapulgites and the mixed layer clays. Typical examplesof specific clays belonging to these classes are the smectites, kaolins,illites, chlorites, attapulgites and mixed layer clays. Smectites, forexample, include montmorillonite, bentonite, pyrophyllite, hectorite,saponite, sauconite, nontronite, talc, beidellite, volchonskoite andvermiculite. Kaolins include kaolinite, dickite, nacrite, antigorite,anauxite, halloysite, indellite and chrysotile. Illites includebravaisite, muscovite, paragonite, phlogopite and biotite. Chloritesinclude corrensite, penninite, donbassite, sudoite, pennine andclinochlore. Attapulgites include sepiolite and polygorskyte. Mixedlayer clays include allevardite and vermiculitebiotite. Variants andisomorphic substitutions of these layered clay minerals offer uniqueapplications.

[0043] The layered clay minerals of the present invention may be eithernaturally occurring or synthetic. Some embodiments of the presentinvention may use natural or synthetic hectorites, montmorillonites andbentonites. Other embodiments may use hectorites clays commerciallyavailable. Typical sources of commercial hectorites are the LAPONITESfrom Southern Clay Products, Inc., U.S.A.; Veegum Pro and Veegum F fromR. T. Vanderbilt, U.S.A.; and the Barasyms, Macaloids and Propaloidsfrom Baroid Division, National Read Comp., U.S.A.

[0044] The inorganic metal oxides of the present invention may besilica- or alumina-based nanoparticles that are naturally occurring orsynthetic. Aluminum can be found in many naturally occurring sources,such as kaolinite and bauxite. The naturally occurring sources ofalumina are processed by the Hall process or the Bayer process to yieldthe desired alumina type required. Various forms of alumina arecommercially available in the form of Gibbsite, Diaspore, and Boehmitefrom manufactures such as Condea.

[0045] Natural Clays—Natural clay minerals typically exist as layeredsilicate minerals and less frequently as amorphous minerals. A layeredsilicate mineral has SiO₄ tetrahedral sheets arranged into atwo-dimensional network structure. A 2:1 type layered silicate mineralhas a laminated structure of several to several tens of silicate sheetshaving a three layered structure in which a magnesium octahedral sheetor an aluminum octahedral sheet is sandwiched between two sheets ofsilica tetrahedral sheets.

[0046] A sheet of an expandable layer silicate has a negative electriccharge, and the electric charge may be neutralized by the existence ofalkali metal cations and/or alkaline earth metal cations. Smectite orexpandable mica can be dispersed in water to form a sol with thixotropicproperties. Further, a complex variant of the smectite type clay can beformed by the reaction with various cationic organic or inorganiccompounds. As an example of such an organic complex, an organophilicclay in which a dimethyldioctadecyl ammonium ion(a quaternary ammoniumion) may be introduced by cation exchange and has been industriallyproduced and used as a gellant of a coating.

[0047] Synthetic Clays—With appropriate process control, the processesfor the production of synthetic nanoscale powders (i.e. synthetic clays)does indeed yield primary particles, which are nanoscale. However, theparticles are not usually present in the form of discrete particles, butinstead predominantly assume the form of agglomerates due toconsolidation of the primary particles. Such agglomerates may reachdiameters of several thousand nanometers, such that the desiredcharacteristics associated with the nanoscale nature of the particlescannot be achieved. The particles may be deagglomerated, for example, bygrinding as described in EP-A 637,616 or by dispersion in a suitablecarrier medium, such as water or water/alcohol and mixtures thereof.

[0048] The production of nanoscale powders such as layered hydroussilicate, layered hydrous aluminum silicate, fluorosilicate,mica-montmorillonite, hydrotalcite, lithium magnesium silicate andlithium magnesium fluorosilicate are common. An example of a substitutedvariant of lithium magnesium silicate is where the hydroxyl group ispartially substituted with fluorine. Lithium and magnesium may also bepartially substituted by aluminum. In fact, the lithium magnesiumsilicate may be isomorphically substituted by any member selected fromthe group consisting of magnesium, aluminum, lithium, iron, chromium,zinc and mixtures thereof.

[0049] Synthetic hectorite was first synthesized in the early 1960's andis now commercially marketed under the trade name LAPONITE™ by SouthernClay Products, Inc. There are many grades or variants and isomorphoussubstitutions of LAPONITE™ marketed. Examples of commercial hectoritesare Lucentite SWN™, LAPONITE S™, LAPONITE XLS™, LAPONITE RD™ andLAPONITE RDS™. One embodiment of this invention uses LAPONITE XLS™having the following characteristics: analysis (dry basis) SiO₂ 59.8%,MgO 27.2%, Na₂O 4.4%, Li₂O 0.8%, structural H₂O 7.8%, with the additionof tetrasodium pyrophosphate (6%); specific gravity 2.53; bulk density1.0.

[0050] Synthetic hectorites, such as LAPONITE RD™, do not contain anyfluorine. An isomorphous substitution of the hydroxyl group withfluorine will produce synthetic clays referred to as sodium magnesiumlithium fluorosilicates. These sodium magnesium lithium fluorosilicates,marketed as LAPONITE™ and LAPONITE S™, contain fluoride ions of UP TOapproximately 10% by weight. It should be understood that the fluorideion content useful in the compositions described herein can comprise anywhole or decimal numeric percentage between 0 and 10% or more. LAPONITEB™, a sodium magnesium lithium fluorosilicate, has a flat, circularplate-like shape, and may have a diameter with a mean particle size,depending on fluoride ion content, that is any number (or narrower setof numbers) that is within the range of between about 25-100 nanometers.For example, in one non-limiting embodiment, LAPONITE B™ may be betweenabout 25-40 nanometers of about 25 nanometers in diameter and about 1nanometer in thickness. Another variant, called LAPONITE S™, containsabout 6% of tetrasodium pyrophosphate as an additive. In some instances,LAPONITE B™ by itself is believed, without wishing to be bound to anyparticular theory, to be capable of providing a more uniform coating(that is, more continuous, i.e., less openings in the way the coatingforms after drying), and can provide a more substantive (protective ordurable) coating than some of the other grades of LAPONITE™ bythemselves (such as LAPONITE RD™). The coating may form at least onelayer of nanoparticles on the dishware surface which has been coated,and may be substantially uniform.

[0051] The ratio of the largest dimension of a particle to the smallestdimension of a particle is known as the particle's aspect ratio. Theaspect ratio of the nanoparticles, in some cases, is of interest informing coatings with the desired characteristics. The average aspectratio of individual particles of LAPONITE™ B is approximately 20-40 andthe average aspect ratio of individual particles of LAPONITE™ RD isapproximately 10-15. A high aspect ratio is desirable for coatingformation using nanosized clay materials. The aspect ratio of thedispersed particles in a suitable carrier medium, such as water is alsoof interest. The aspect ratio of the particles in a dispersed medium canbe considered to be lower where several of the particles are aggregatedthan in the case of individual particles. The aspect ratio ofdispersions can be adequately characterized by TEM (transmissionelectron microscopy). LAPONITE B™ occurs in dispersions as essentiallysingle clay particles or stacks of two clay particles. The LAPONITE RD™occurs essentially as stacks of two or more single clay particles. Thus,the aspect ratio of the particles dispersed in the carrier medium can beaffected if there is an aggregation of individual particles. In certainnon-limiting embodiments, it may be desirable for at least some of (andpreferably a plurality of) individual (non-aggregated) platelet anddisc-shaped non-photoactive nanoparticles to have at least one dimensionthat is greater than or equal to about 0.5 nanometers, and an aspectratio of greater than or equal to about 15. The aspect ratio of LAPONITEB™ is about 20-40 and the aspect ratio of LAPONITE RD™ is less than 15.Larger aspect ratios are preferred for platelet and disc-shapedparticles than for rod-shaped particles.

[0052] The aspect ratio of rod-shaped particles, such as small boemitealumina (e.g., Disperal P2™), can be lower than the disc-shaped orplatelet-shaped particles while maintaining adequate coating-formingproperties. In certain non-limiting embodiments, it may be desirable forat least some of (and preferably a plurality of) the individualrod-shaped non-photoactive nanoparticles to have at least one dimensionthat is greater than or equal to about 0.5 nanometers, and an aspectratio of greater than or equal to about 3.

[0053] LAPONITE™ has the formula:

[Mg_(w)Li_(x)Si₈O₂₀OH_(4−y)F_(y)]^(z−)

[0054] wherein w=3 to 6, x=0 to 3, y=0 to 4, z=12−2w−x, and the overallnegative lattice charge may be balanced by counter-ions; and wherein thecounter-ions are selected from the group consisting of selected Na⁺, K⁺,NH₄ ⁺, Cs⁺, Li⁺, Mg⁺⁺, Ca⁺⁺, Ba⁺⁺, N(CH₃)₄ ⁺ and mixtures thereof.

[0055] Depending upon the application, the use of variants andisomorphous substitutions of LAPONITE™ provides great flexibility inengineering the desired properties of the rinse aid surface coatingcomposition of the present invention. LAPONITE B™ and LAPONITE RD™ aloneor in any combination or mixture together will provide the desiredbenefits to dishware surfaces, including both glass and plasticdishware. Not to be limited by theory when LAPONITE B™ and LAPONITE RD™are used in combination, a mixture of weight percentages from about 1:99through about 99:1 of LAPONITE B™ to LAPONITE RD™ can be used in thisinvention. The individual platelets of LAPONITE™ are negatively chargedon their faces and possess a high concentration of surface bound water.When applied to a dishware surface, the dishware surface may behydrophilically modified and exhibits surprising and significantlyimproved wetting and sheeting, uniform drying, anti-spotting,anti-staining, anti-filming, self cleaning, and durability properties.

[0056] In addition, the LAPONITE™ modified surface exhibits some“self-cleaning” properties (food removal via water rinsing, e.g. fromautomatic dishwasher sprayer) and/or stain release benefits (top layersare strippable via mild mechanical action). The hydrophilicity can alsoprovide the exposed layer of nanoparticles with resistance to stainingby hydrophobic types of stains.

[0057] In contrast to hydrophilic modification with organic polymers,benefits provided by LAPONITE™, either alone or in combination with acharged modifier, are longer lived. For example, sheeting/anti-spottingbenefits are maintained on dishware after multiple rinses in anautomatic dishwasher versus one rinse with tap water versus on adishware surface coated with current hydrophilic polymer technology.

[0058] Inorganic Metal Oxides—Inorganic metal oxides generally fallwithin two groups-photoactive and non-photoactive nanoparticles. Not tobe limited by theory, photoactive nanoparticles are not generally usedin automatic dishwashing environments.

[0059] Non-photoactive metal oxide nanoparticles do not use UV orvisible light to produce the desired effects. Examples ofnon-photoactive metal oxide nanoparticles generally include but are notlimited to silica and alumina. A non-limiting embodiment of the presentinvention comprises a mixture of inorganic metal oxides, natural and/orsynthetic clays.

[0060] Boehmite alumina is a water dispersible, inorganic metal oxidehaving a mean particle size of about 25 nanometers in diameter and about2-4 nanometers in thickness. Such product is commercially available, forexample, under the trade name Disperal P2™.

[0061] Inorganic metal oxide nanoparticle provide an additional benefitabove those of the layered clays where concentrated sols of inorganicmetal oxides can be prepared without gelling. This may be particularlyadvantageous for applications that utilize a dilution step prior toapplication of the rinse aid surface coating composition. Additionally,inorganic metal oxide nanoparticles can provide tolerance to hard waterused in making nanoparticle dispersions, diluting nanoparticlesdispersion compositions, and the application of nanoparticlecompositions wherein the dishware surface contains hard water ions.

Non-photoactive Nanoparticle Surface Modification as a Rinse Aid

[0062] Non-photoactive nanoparticle surface modification of dishwareprovide rinse aid benefits such as improved: wetting and sheeting,uniform drying, anti spotting, self cleaning, and durability to alltypes of dishware surfaces. Deposition of the non-photoactivenanoparticle surface coating composition comprising non-photoactivenanoparticles on the dishware surface can make the dishware surface morehydrophilic. Hydrophilic non-photoactive nanoparticle surfacemodification of glass, metal and plastic dishware surfaces has beenconfirmed by analytical methods.

[0063] Significant differences have been observed in the rinse aidsurface coating formation behavior on dishware surfaces treated withdifferent non-photoactive nanoparticles like synthetic hectorites (e.g.sodium magnesium lithium fluorosilicate versus sodium magnesium lithiumsilicates). For example, LAPONITE B™, a sodium magnesium lithiumfluorosilicate, forms a better homogeneous coating on glass surfacesthan LAPONITE RD™, a sodium magnesium lithium silicate. This has beenconfirmed by analytical technique using an Atomic Force Microscope(AFM). The isomorphous substitution of the hydroxyl group with fluorinein LAPONITE B™, when applied as a layer onto glass surfaces, providesimproved filming and spotting benefits on treated glass surfacesrelative to glassware treated with LAPONITE RD™without the hydroxylgroup-fluorine substitution. Thus, LAPONITE B™ may be an alternative,non-photoactive nanoparticle surface modifying agent for impartingfilm/spot/shine benefits to glassware.

[0064] In contrast, plastic dishware treated with LAPONITE RD™ providessurprisingly better dishware care benefits than plastic dishware treatedwith LAPONITE B™. It appears that LAPONITE RD™, without the hydroxylgroup-fluorine substitution, may be more substantive than LAPONITE B™and thus provides better cleaning through greater durability of thesurface modification agent on plastic dishware relative to plasticdishware treated with LAPONITE B™ in subsequent washes. Non-photoactivenanoparticle surface modification on plastic dishware provides reducedtomato staining and improved cleaning of plastic dishware covered withspaghetti. Other benefits include improved uniform drying and selfcleaning properties of the plastic surfaces treated with non-photoactivenanoparticles in rinse aid applications.

[0065] For dishware rinse aid application in automatic dishwashingappliances, the prevention of non-photoactive nanoparticle gel formationmay be important to this invention. Without dispersants, LAPONITE™ insolution at a concentration 1% or above forms a gel on standing. Theaddition of a dispersant, like polyacrylate at 0.5-2%, to thenon-photoactive nanoparticle surface coating composition prevents gelformation. Polyacrylates, acrylic acid/maleic acid copolymers ormixtures of polyacrylates and acrylic acid/maleic acid copolymers notonly prevent gel formation in non-photoactive nanoparticle surfacecoating compositions, these dispersant polymers actually help improvefilm/spot benefits of treated dishware articles particularly at highwater hardness levels, such as 3.3 mM (Calcium:Magnesium=3:1).

[0066] Improved hardness tolerance of the non-photoactive nanoparticlesystem may be observed when dishware articles are treated with LAPONITEB™ in combination with dispersant polymers. As a result of thissurprising hardness tolerance, LAPONITE B™ in combination with adispersant polymer may be an alternative, non-photoactive nanoparticlesystem for imparting improved film/spot/shine benefits to dishwaresurfaces at high water hardness.

[0067] Non-photoactive nanoparticle surface modification also providesimproved glass care benefits such as prevention of surface damage andimproved surface smoothness. Glassware treated with LAPONITE B™ providessignificantly better glass care benefits than glassware treated withLAPONITE RD™. LAPONITE B™ treatment provides a better protective layeron glassware surfaces LAPONITE RD™ and prevents damage to these surfacesin subsequent washes. It also has been show to provide improved surfacesmoothness. It is to be noted that no build-up of LAPONITE B™ takesplace with multiple washes.

Charged Functionalized Molecules

[0068] Hydrophilic modification can be augmented via use ofnanoparticles such as LAPONITE™ as a basecoat or primer and thentreating the negatively charged surface with functionalized chargedmolecules as a two-step process.

[0069] The functionalized surface molecules may comprise at least twodifferent types of functionalized surface molecules. Chargedfunctionalized surface molecules may be selected from the groupconsisting of polymers, copolymers, surfactants and mixtures thereof.Functionalized surface molecules can also be selected from the groupconsisting of multi-valent inorganic salts consisting of Ca⁺², Mg⁺²,Ba⁺², Al⁺³, Fe⁺², Fe⁺³, Cu⁺² and mixtures thereof, where an appropriateanion may be used to balance the charge.

[0070] Sequential layering of LAPONITE™ and ethoxylated, quaternizedoligoamines results in a reduction in the contact angles, and enhancedsheeting/wetting of the treated dishware surface. Moreover, if thecharged functionalized molecule species possess a lipophilic component,the LAPONITE treated dishware surface can be hydrophobically modified.Net, the combination of nanoclay plus charge functionalized moleculesprovides a novel technique for tailoring the hydrophilic/lipophiliccharacter of a dishware surface.

[0071] Similarly, hydrophilic modification can be augmented via use ofalumina as a basecoat or primer and then treating the positively chargeddishware surface with functionalized charged molecules as a two-stepprocess. Specifically, sequential layering of alumina and hydrophilicanionic polymers results in enhanced sheeting/wetting of the treateddishware surface. Moreover, if the charged functionalized moleculespecies possess a lipophilic component, the alumina treated dishwaresurface can be hydrophobically modified. Net, the combination ofinorganic metal oxides plus charge functionalized molecules provides anovel technique for tailoring the hydrophilic/lipophilic character of adishware surface.

I. COMPOSITION

[0072] If the coating is in the form of a composition, the rinse aidsurface coating composition may be present in any form, such as liquids(aqueous or non-aqueous), granules, pastes, powders, spray, foam,tablets, gels, and the like. Granular compositions can be in “compact”form and the liquid compositions can also be in a “concentrated” form.The rinse aid surface coating compositions of the present inventionencompass compositions that are used on substrates having any suitabledishware surface including, but not limited to: plastics, metals, glass,wood, coated surfaces, glazed surfaces and mixtures thereof.

[0073] In one embodiment, the rinse aid surface coating compositioncomprises: (a) an effective amount of non-photoactive nanoparticles; (b)optionally one or more adjunct ingredients; and (c) optionally asuitable carrier medium.

[0074] The rinse aid material for coating the dishware surfaces cancomprise a plurality of non-photoactive nanoparticles, or it cancomprise a single non-photoactive nanoparticle surface coatingcomposition. Such a rinse aid surface coating composition may comprise:(a) an effective amount of non-photoactive nanoparticles; (b) adispersant polymer; (c) optionally a surfactant; (d) optionally apH-adjusting agent; (e) optionally having associated to saidnanoparticle surface a quantity of one or more functionalized surfacemolecules exhibiting properties selected from the group consisting ofhydrophilic, hydrophobic and mixtures thereof; (f) optionally one ormore adjunct ingredients; and (g) optionally a suitable carrier medium.

[0075] In another embodiment of the present invention, there may beprovided a rinse aid surface coating composition for coating thedishware surfaces comprising (a) an effective amount of non-photoactivenanoparticles; (b) a dispersant polymer selected from the groupconsisting of polyacrylic acid, poly (acrylic/allyl alcohol), poly(acrylic/maleic), polycarboxylic acids, sodium tripolyphosphate,pyrophosphate, and mixtures thereof; (c) optionally a surfactant; (d)optionally a pH-adjusting agent; (e) optionally having associated tosaid nanoparticle surface a quantity of one or more functionalizedsurface molecules exhibiting properties selected from the groupconsisting of hydrophilic, hydrophobic and mixtures thereof; (f)optionally one or more adjunct ingredients; and (g) optionally asuitable carrier medium.

[0076] In another embodiment of the present invention, there may beprovided a rinse aid surface coating composition for coating thedishware surfaces comprising (a) an effective amount of non-photoactivenanoparticles wherein the photoactive nanoparticles are selected fromthe group consisting of Lucentite SWN™, LAPONITE B™, LAPONITE S™,LAPONITE XLS™, LAPONITE RD™ and LAPONITE RDS™, and mixtures thereof; (b)a dispersant polymer; (c) optionally a surfactant; (d) optionally apH-adjusting agent; (e) optionally having associated to saidnanoparticle surface a quantity of one or more functionalized surfacemolecules exhibiting properties selected from the group consisting ofhydrophilic, hydrophobic and mixtures thereof; (f) optionally one ormore adjunct ingredients; and (g) optionally a suitable carrier medium.

[0077] In another embodiment of the present invention, there may beprovided a rinse aid surface coating composition for coating thedishware surfaces comprising (a) an effective amount of non-photoactivenanoparticles wherein the photoactive nanoparticles are selected fromthe group consisting of LAPONITE RD™ and LAPONITE B™, and mixturesthereof; (b) a dispersant polymer selected from the group consisting ofpolyacrylic acid, poly (acrylic/allyl alcohol), poly (acrylic/maleic),polycarboxylic acids, sodium tripolyphosphate, pyrophosphate, andmixtures thereof; (c) optionally a surfactant; (d) optionally apH-adjusting agent; (e) optionally having associated to saidnanoparticle surface a quantity of one or more functionalized surfacemolecules exhibiting properties selected from the group consisting ofhydrophilic, hydrophobic and mixtures thereof; (f) optionally one ormore adjunct ingredients; and (g) optionally a suitable carrier medium.

[0078] In one embodiment, the rinse aid surface coating compositioncomprises: (a) an effective amount of non-photoactive nanoparticles; (b)a dispersant polymer; (c) a surfactant; (d) a pH-adjusting agent; (d)optionally one or more adjunct ingredients; and (e) a suitable carriermedium. surface.

[0079] Alternatively, an effective amount of one or more nanoparticlesdescribed above are included in compositions useful for coating avariety of dishware surfaces in need of treatment. As used herein,“effective amount of one or more nanoparticles” refers to the quantityof nanoparticles of the present invention described hereinbeforenecessary to impart the desired dishware surface coating benefit in thespecific composition (for example, an amount effective to provide aresidual hydrophilic coating on a dishware surface). Such effectiveamounts are readily ascertained by one of ordinary skill in the art andmay be based on many factors, such as the particular nanoparticle used,the dishware surface coating application, the specific composition ofthe rinse aid surface coating composition, and whether a liquid or dry(e.g., granular, powder) composition may be required, and the like.

[0080] An effective amount of a non-photoactive nanoparticles in thepresent invention, such as a natural clay, synthetic clay or aninorganic metal oxide, requires that at least 10% of the target dishwaresurface may be modified to effect the desired benefits.

[0081] The concentration of nanoparticles in the rinse aid material orthe compositions described herein can range all the way up to 100%. Anon-limiting example of the use of nanoparticles in such a highconcentration would be if the nanoparticles alone were applied in theform of a powder to the dishware surface to be treated.

[0082] The nanoparticle coating compositions described herein canprovide the desired performance on all dishware surfaces within theautomatic dishwashing appliance, including vertical dishware surfaces,even when relatively small quantities of the composition are used. Forexample, it may be possible to coat a vertical dishware surface with thenanoparticle coating composition in amounts of less than or equal toabout 25 micrograms of nanoparticles/cm² of the surface, oralternatively any number of micrograms less than 25 (e.g., 20, 15, 10,5, 0.5, etc.). In other alternatives, the coat weight of nanoparticleson the dishware surface can be expressed in terms of a range, includingbut not limited to any range of numbers, without the need for specifyingthe same, that may be less the above coat weight (25 micrograms ofnanoparticles/cm²). The rinse aid surface coating compositions can, as aresult, be applied in the more convenient and economical form of adilute liquid, rather than as a gel. The rinse aid surface coatingcompositions in such embodiments, since applied as a thin layer, willquickly dry on the dishware surface, and will not run or drip down avertical dishware surface. (Of course, in other embodiments, higher coatweights could be used.)

[0083] In one non-limiting aspect of the present invention, theconcentration of nanoparticles in the rinse aid surface coatingcomposition prior to application to dishware surfaces may be less thanor equal to about 50% by weight of the rinse aid surface coatingcomposition, or any number less than 50% of the weight of the rinse aidsurface coating composition (e.g., less than or equal to about 20% toless than or equal to about 1%, or less, for example when the rinse aidsurface coating composition is a liquid that is sprayed onto thedishware surface; alternatively, less than or equal to about 0.5%,alternatively less than or equal to about 0.1%).

[0084] In one aspect of the present invention, the rinse aid surfacecoating composition may be prepared by dispersing the dry nanoparticlepowder into deionized water to form a 1% concentrated mixture. Thismixture may then be applied to said dishware surface by either spraying,dipping, painting, wiping, or other manner in order to deliver a rinseaid coating especially a transparent coating that covers at least 10%and/or alternatively at least 30% and/or alternatively at least 50%and/or alternatively at least 80% and/or alternatively at least 100% ofsaid dishware surface.

[0085] In other embodiments, the rinse aid surface coating compositionis prepared by dispersing the dry nanoparticle powder with a surfactantand a dispersant into tap water. Two non-limiting examples of such acoating composition are provided in the Examples section at the end ofthis description. Examples of other suitable dispersants include, butare not limited to: polyacrylic acid, poly (acrylic/allyl alcohol), poly(acrylic/maleic), polycarboxylic acids, sodium tripolyphosphate,pyrophosphate, and mixtures thereof; and the other dispersants andbuilders described herein. This mixture is then applied to said surfaceby either spraying, dipping, painting, wiping, or other manner in orderto deliver a coating especially a transparent coating that covers atleast 10% and/or alternatively at least 30% and/or alternatively atleast 50% and/or alternatively at least 80% and/or alternatively atleast 100% of said surface.

[0086] In another embodiment of the present invention, the rinse aidsurface coating composition may be prepared by diluting a nanoparticlegel with deionized water to form a 1% concentrated mixture. This mixturemay then be applied to said dishware surface by either spraying,dipping, painting, wiping, or other manner in order to deliver atransparent coating that covers at least 10% and/or alternatively atleast 30% and/or alternatively at least 50% and/or alternatively atleast 80% and/or alternatively at least 100% of said dishware surface.

[0087] In another embodiment of the present invention, the rinse aidsurface coating composition may be prepared by diluting a 10%concentrated boehmite alumina (e.g. Disperal P2™ from Condea, Inc.)coating composition with deionized water to form a 0.1% concentratedmixture. This mixture may then be applied to said dishware surface byeither spraying, dipping, painting, wiping, or other manner in order todeliver a rinse aid surface coating especially a transparent coatingthat covers at least 10% and/or alternatively at least 30% and/oralternatively at least 50% and/or alternatively at least 80% and/oralternatively at least 100% of said dishware surface.

[0088] In another embodiment of the present invention, the rinse aidsurface coating composition may be prepared by diluting a 1%concentrated sodium magnesium lithium fluorosilicate (e.g. LAPONITE B™from Southern Clay Products, Inc.) coating composition with deionizedwater to form a 0.1% concentrated mixture. This mixture may then beapplied to said dishware surface by either spraying, dipping, painting,wiping, or other manner in order to deliver a rinse aid surface coatingespecially a transparent coating that covers at least 10% and/oralternatively at least 30% and/or alternatively at least 50% and/oralternatively at least 80% and/or alternatively at least 100% of saiddishware surface.

[0089] In another embodiment of the present invention, the rinse aidsurface coating composition may be prepared by diluting a 1%concentrated lithium magnesium sodium silicate (e.g. Lucentite SWN™ fromKobo Products, Inc.) coating composition with deionized water to form a0.1% concentrated mixture. This mixture may then be applied to saiddishware surface by either spraying, dipping, painting, wiping, or othermanner in order to deliver a rinse aid surface coating especially atransparent coating that covers at least 10% and/or alternatively atleast 30% and/or alternatively at least 50% and/or alternatively atleast 80% and/or alternatively at least 100% of said dishware surface.

[0090] In another embodiment of the present invention, the rinse aidsurface coating composition may be prepared by dispersing the drynanoparticle powder into deionized water to form a 0.1% concentratedmixture. This mixture may then be applied to said dishware surface byeither spraying, dipping, painting, wiping, or other manner in order todeliver a rinse aid surface coating especially a transparent coatingthat covers at least 10% and/or alternatively at least 30% and/oralternatively at least 50% and/or alternatively at least 80% and/oralternatively at least 100% of said dishware surface.

[0091] In other embodiments, the rinse aid surface coating compositionmay be prepared by dispersing the dry nanoparticle powder with asurfactant and a dispersant into tap water, so that the use of deionizedwater may not be necessary. Two non-limiting examples of such a rinseaid surface coating composition are provided in the Examples section atthe end of this description. Examples of other suitable dispersantsinclude, but are not limited to: polyacrylic acid, poly (acrylic/allylalcohol), poly (acrylic/maleic), polycarboxylic acids, sodiumtripolyphosphate, pyrophosphate, and mixtures thereof; and the otherdispersants and builders described herein. This mixture may then beapplied to said dishware surface by either spraying, dipping, painting,wiping, or other manner in order to deliver a rinse aid surface coatingespecially a transparent coating that covers at least 10% and/oralternatively at least 30% and/or alternatively at least 50% and/oralternatively at least 80% and/or alternatively at least 100% of saiddishware surface.

[0092] In one non-limiting aspect, an effective amount of chargedfunctionalized dishware surface molecules that provide hydrophobicproperties to the nanoparticle surface, generally modifies from about 1%to about 100% of the nanoparticle surface or from about 0.01 to about 5%by weight of the rinse aid surface coating composition.

[0093] In other embodiments, rather than modifying the characteristic ofthe dishware surface to be coated, the charged functionalized moleculescan be used to aid in the delivery of the nanoparticles to the dishwaresurface to be coated. For instance, in one non-limiting embodiment, asurfactant could be mixed with the nanoparticles in order to aid in thedelivery of the nanoparticles to the dishware surface to be coated incases in which it may be difficult to combine the nanoparticle coatingwith another carrier medium, or in which it may be difficult to applythe nanoparticles to a particular dishware surface.

[0094] Several non-limiting examples of various coatings and coatingcompositions wherein the nanoparticles of the present invention may beemployed are discussed in further detail below. Also, the rinse aidsurface coating compositions may include from about 0.001% to about99.999%, alternatively from about 0.01% to about 99.99% by weight of therinse aid surface coating composition of the adjunct materials. Incertain embodiments, the rinse aid surface coating composition comprisesless than or equal to about 10% (or less than about 10%) by weight ofother optional ingredients other than the nanoparticles and the carriermedium, alternatively, less than or equal to any percentage less than 10(e.g., less than or equal to about 5%, alternatively less than or equalto about 1%), of other ingredients. As used herein, other optionalingredients are those other than the non-photoactive nanoparticles,carrier medium, dispersant polymers, funtionalized molecules,surfactants, wetting agents and pH-adjusting agents disclosedseparately.

[0095] As used herein, the coatings and “coating compositions” includehand and appliance applied coatings, compositions, including additivecoatings, additive compositions, and compositions suitable for use inthe soaking and/or pretreatment of unclean or stained dishware surfaces.The rinse aid surface coatings, coating compositions and/or methodsand/or articles of manufacture of the present invention can be used forall uses including manufacturing, commercial, industrial, institutional,agricultural and/or for domestic use.

[0096] The rinse aid surface coating compositions of the presentinvention can also be used as detergent additive products in solid orliquid form. Such additive products are intended to supplement or boostthe performance of conventional coating compositions used to cleandishware surfaces and can be added at any stage of the automaticdishwashing cleaning process, however addition of the transparent rinseaid surface coating composition to a clean dishware surface may be moreeffective.

[0097] Coating compositions according to the present invention can alsobe in a “concentrated form”, in such case, the concentrated liquid,coating compositions according the present invention will contain alower amount of a suitable carrier medium, compared to conventionalliquid, coating compositions. Typically the suitable carrier mediumcontent of the concentrated system, rinse aid surface coatingcomposition may be alternatively 99.99 to 50% by weight of the rinse aidsurface coating composition.

[0098] Coating compositions according to the present invention can alsobe in a “concentrated form” that may be compatible with “untreated tapwater”, in such case, the concentrated liquid, coating compositionsaccording the present invention will contain a lower amount of asuitable carrier medium, compared to conventional liquid, coatingcompositions and a dispersant. Typically the suitable carrier mediumcontent of the concentrated system, rinse aid surface coatingcomposition may be alternatively 99.99 to 50% by weight of the rinse aidsurface coating composition. Typically the dispersant content of theconcentrated system, rinse aid surface coating composition may bealternatively 0.001 to 10 %.

[0099] The present invention includes liquid (with a compatible carrier)and rinse aid surface coating compositions, including aqueous liquid,rinse aid surface coating compositions. Rinse aid surface coatingcompositions alternatively comprise in addition to the nanoparticlesystem described hereinabove, about 50% to about 99.99%, alternativelyfrom about 80% to about 99.99%, by weight of a liquid carrier orsuitable carrier medium, such as an alcohol and/or water.

[0100] The rinse aid surface coating compositions of the presentinvention also may include one or more adjunct materials. The term“adjunct materials”, as used herein, means any liquid, solid or gaseousmaterial selected for coating compositions, alternatively compatiblewith the other ingredients present in the coating compositions of thepresent invention.

[0101] The specific selection of adjunct materials may be readily madeby considering the dishware surface to be coated. Examples of suitableadjunct materials include, but are not limited to, surfactants,builders, bleaches, bleach activators, bleach catalysts, enzymes, enzymestabilizing systems, chelants, optical brighteners, stain releasepolymers, dye transfer agents, dispersants, suds suppressors, dyes,perfumes, colorants, filler salts, hydrotropes, photoactivators,fluorescers, conditioners, hardening agents, hydrolyzable surfactants,preservatives, anti-oxidants, anti-wrinkle agents, germicides,fungicides, color speckles, silvercare, anti-tarnish and/oranti-corrosion agents, alkalinity sources, solubilizing agents,carriers, processing aids, pigments and pH control agents as describedin U.S. Pat. Nos. 5,705,464; 5,710,115; 5,698,504; 5,695,679; 5,686,014and 5,646,101. Specific adjunct materials are exemplified in detailhereinafter.

[0102] If the adjunct materials are not compatible with the otheringredients present in the coating compositions of the presentinvention, then suitable methods of keeping the incompatible adjunctmaterials and the other ingredients separate (not in contact with eachother) until combination of the two components may be appropriate can beused. Suitable methods can be any method known in the art, such asgelcaps, encapsulation, tablets, physical separation, etc.

[0103] The rinse aid surface coating compositions of the presentinvention can comprise: (a) an effective amount of non-photoactivenanoparticles; (b) optionally a surfactant; (c) optionally havingassociated to said nanoparticle surface a quantity of one or morefunctionalized surface molecules exhibiting properties selected from thegroup consisting of hydrophilic, hydrophobic and mixtures thereof; (d)optionally an effective amount of photoactive nanoparticles; (e)optionally one or more adjunct ingredients; and (f) a suitable carriermedium.

[0104] The rinse aid surface coating compositions of the presentinvention can also be used as detergent additive products in liquid formfor automatic dishwashing appliances. Such additive products areintended to supplement or boost the performance of conventional coatingcompositions and can be added at any stage of the dishwashing process,however, best results are achieved in the rinsing cycle.

[0105] Further, the rinse aid surface coating compositions according tothe present invention may be isotropic (clear, single phase) liquids,aqueous gels, phase-separated liquid compositions and/or colored liquidcompositions.

[0106] In certain embodiments, the rinse aid surface coatingcompositions are non-thixotropic. That is, the rinse aid surface coatingcompositions, in such embodiments, do not have a different state when atrest (such as a gel, when they are not under shear load) than whenactivated (such as a liquid, when under shear load), such that the rinseaid surface coating composition tends to return to its at rest state(e.g., a gel) after the shear load is removed. For the purposes of thisdescription, a rinse aid surface coating composition will not beconsidered to be thixotropic if it is placed in another state in othermanners, such as by diluting a gel coating composition with anothermaterial to form a liquid.

[0107] The rinse aid surface coating compositions according to thepresent invention may be of any suitable viscosity. The viscosity of therinse aid surface coating compositions should be such that they are ableto be effectively applied to the dishware surface to be coated. Thus,for instance, if the rinse aid surface coating compositions are to beapplied to a dishware surface that has portions that are sloped (theirslope has a vertical component), the rinse aid surface coatingcomposition should either be applied in a relatively low quantities thatthey are able to dry on the dishware surface without running off asdiscussed above, or if applied in greater quantities, they should nothave such a low viscosity that the rinse aid surface coating compositionruns off the dishware surface to be coated. Non-limiting examples ofsuitable viscosities are less than or equal to about 1,000 Cps at 100rpm, or any increment of 10 less than 1,000 (including, but not limitedto 100 Cps, 40 Cps, and 1 Cps (the latter being the viscosity ofwater)).

[0108] The dry surface coating compositions of the present invention cancomprise: (a) an effective amount of non-photoactive nanoparticles; (b)optionally a surfactant; (c) optionally having associated to saidnanoparticle surface a quantity of one or more functionalized surfacemolecules exhibiting properties selected from the group consisting ofhydrophilic, hydrophobic and mixtures thereof; (d) optionally one ormore adjunct ingredients; and (e) an optionally, a suitable carriermedium.

[0109] The dry surface coating compositions of the present invention canalso be used as detergent additive products in powder, granule or tabletform for automatic dishwashing appliances. Such additive products areintended to supplement or boost the performance of conventional coatingcompositions and can be added at any stage of the dishwashing process,however, best results are achieved in the rinsing cycle.

[0110] Further, the dry surface coating compositions according to thepresent invention may be in powder, granule, tablet or encapsulatedcomplex form.

Suitable Carrier Medium

[0111] The carrier medium can form part of the rinse aid surface coatingcomposition, or it can comprise the medium in which the nanoparticlesare carried (or transported) for application to the dishware surface.Several non-limiting examples of types of carrier mediums are providedby way of explanation, and not by way of limitation. In one example, therinse aid surface coating composition can be provided in the form of anaqueous liquid in a container, and the liquid can be sprayed onto adishware surface. In such a case, the aqueous liquid carrier in thecontainer holding the rinse aid surface coating composition may bereferred to herein as the “static carrier”. When this coatingcomposition is sprayed onto the dishware surface, the liquid droplets inthe spray may be referred to herein as the “dynamic carrier” (the mediumthat transports the nanoparticles to the dishware surface in order tocontact the dishware surface). In another example, the rinse aid surfacecoating composition may exist in a gel form in a container (the gelwould be the form of the static carrier) and the gel could be dilutedwith water and sprayed as a liquid onto the dishware surface (in whichcase the liquid spray would be the dynamic carrier). The term “carrier”,as used herein, includes both static and dynamic carriers.

[0112] Suitable carrier mediums include liquids, solids and gases. Onesuitable carrier medium may be water, which can be distilled, deionized,or tap water. Water may be valuable due to its low cost, availability,safety, and compatibility. In other embodiments in which the carriermedium may be aqueous, at least some of the aqueous carrier may bepurified beyond the treatment it received to convert it to tap water(that is, the tap water may be post-treated, e.g., deionized ordistilled). The purified water could comprise: all or part of the staticcarrier for the composition; all or part of the dynamic carrier; or, allor part of both. Though aqueous carrier mediums are more common thandry, non-aqueous mediums, the present invention can exist as a drypowder, granule or tablet or encapsulated complex form. In otherembodiments in which the carrier medium may be tap water, wherein atleast some of the carrier may be hard water having a hardness of atleast 3.3 mM (Calcium:Magnesium=3:1).

[0113] Optionally, in addition to water, the carrier can contain a lowmolecular weight organic solvent that may be highly soluble in water,e.g., ethanol, methanol, propanol, isopropanol and the like, andmixtures thereof. Low molecular weight alcohols can allow the treateddishware surface to dry faster. The optional water soluble low molecularweight solvent can be used at a level of up to about 50%, typically fromabout 0.1% to about 25%, alternatively from about 2% to about 15%,alternatively from about 5% to about 10%, by weight of the suitablecarrier medium. Factors that need to consider when a high level ofsolvent may be combined with the suitable carrier medium are odor,flammability, dispersancy of the nanoparticle and environment impact.

[0114] In other embodiments, the carrier can be an airstream. Forinstance, the rinse aid material, or the composition can be added into astream of moving air, and the air can convey the non-photoactivenanoparticles to the dishware surface to be treated.

[0115] In other embodiments, the coating material or composition cansimply be dropped through the air by gravity onto the dishware surfaceto be treated (one example of which would be by sifting a solid materialonto the dishware surface).

Classes of Functionalized Surface Molecules Polymer Classes and Examples

[0116] Polymers, used as charged functionalized surface modifying agentsand not as dispersants, are optional ingredients in the compositions ofthe present invention. If desired, the compositions may be substantiallyfree of polymers, when used as charged functionalized surface modifyingagents and not as dispersants.

[0117] If polymers are used as functionalized surface molecules and notas dispersants, one non-limiting aspect of the invention can bedescribed in a two-step process. In such a two-step process, thenanoparticle composition may be applied to the dishware surface to forma layer of nanoparticles on the dishware surface. After this layer isformed and dried, a composition comprising the desired polymers can beapplied to the layer of nanoparticles to further modify thenanoparticle-coated dishware surface. Without wishing to be bound by anyparticular theory, when the polymer composition may be applied in thisway, it is believed that the nanoparticle layer anchors the polymers tothe dishware surface. This can be used to provide the nanoparticlecoated dishware surface with different properties than are provided bythe nanoparticles alone. Using this two-step process may provideadvantages over applying the polymers to the nanoparticles and thenapplying the polymer coated nanoparticles to the dishware surface. Oneadvantage may be that the two-step process provides a more continuouscovering on the dishware surface by virtue of the uniformity of theinitial layer of nanoparticles, than the less continuous structureformed by depositing nanoparticles with polymers attached thereto ontothe dishware surface.

[0118] When not used as dispersants, polymers and copolymers in which atleast one segment or group of the polymer may comprise functionalitythat serves to anchor or enhance adsorption on nanoparticle surfaces.These polymers also comprise at least one segment or group that servesto provide either hydrophilic or hydrophobic character to the polymerwhen adsorbed on a nanoparticle. Note that in some cases, the anchoringsegment may also serve as the functionalizing segment.

[0119] Examples of the anchoring segments or groups include: polyamines,quaternized polyamines, amino groups, quaternized amino groups, andcorresponding amine oxides; zwitterionic polymers; polycarboxylates;polyethers; polyhydroxylated polymers; polyphosphonates andpolyphosphates; and polymeric chelants.

[0120] Examples of the hydrophilizing segments or groups include: watersoluble polyethers; water soluble polyhydroxylated groups or polymers,including saccharides and polysaccharides; water soluble carboxylatesand polycarboxylates; water soluble anionic groups such as carboxylates,sulfonates, sulfates, phosphates, phosphonates and polymers thereof;water soluble amines, quaternaries, amine oxides and polymers thereof;water soluble zwitterionic groups and polymers thereof; water solubleamides and polyamides; and water soluble polymers and copolymers ofvinylimidazole and vinylpyrrolidone.

[0121] Examples of the hydrophobizing segments or groups include: alkyl,alkylene, and aryl groups, and polymeric aliphatic or aromatichydrocarbons; fluorocarbons and polymers comprising fluorocarbons;silicones; hydrophobic polyethers such as poly(styrene oxide),poly(propylene oxide), poly(butene oxide), poly(tetramethylene oxide),and poly(dodecyl glycidyl ether); and hydrophobic polyesters such aspolycaprolactone and poly(3-hydroxycarboxylic acids).

Hydrophilic Surface Polymers

[0122] Examples of hydrophilic surface polymers include, but are notlimited to: thoxylated or alkoxylated polyamines; polycarboxylatedpolyamines; polycarboxylates; polyethers; polyhydroxyl materials;polyphosphates and phosphonates.

Hydrophobic Surface Polymers

[0123] Alkylated polyamines include, but are not limited to:polyethyleneimine alkylated with fatty alkylating agents such as dodecylbromide, octadecyl bromide, oleyl chloride, dodecyl glycidyl ether andbenzyl chloride or mixtures thereof; and polyethyleneimine acylated withfatty acylating agents such as methyl dodecanoate and oleoyl chloride;silicones including, but not limited to: polydimethylsiloxane havingpendant aminopropyl or aminoethylaminopropyl groups and fluorinatedpolymers including, but not limited to: polymers including as monomers(meth)acrylate esters of perfluorinated or highly fluorinated alkylgroups.

Non-Polymeric Materials

[0124] Molecules with at least one segment or group which comprisesfunctionality that serves to anchor or enhance adsorption onnanoparticle surfaces can also be used. These molecules also comprise atleast one segment or group that serves to provide either hydrophilic orhydrophobic character to the molecule when adsorbed on a nanoparticle.Note that in some cases, the anchoring segment may also serve as thehydrophilizing segment.

[0125] Examples of the anchoring segments or groups that may also serveas the hydrophilizing segment include amino groups, quaternized aminogroups, and corresponding amine oxides groups; zwitterionic groups; andcarboxylate groups.

[0126] Examples of the hydrophobizing segments or groups include alkyl,aryl, alkaryl, siloxane, polysiloxane, fluoroether, and fluoroalkylsurfactants with cationic, zwitterionic, semi-polar, nonionic, oranionic head groups.

Examples of Non-Polymeric Surface Modifying Materials

[0127] Fatty amines and quats including: ditallowdimethylammoniumchloride; octadecyltrimethylammonium bromide; dioleyl amine; andBenzyltetradecyldimethylammonium chloride can also be used.

[0128] Examples of fluorocarbon-based surfactants include:1-propanaminium,3-[[(heptadecafluorooctyl)sulfonyl]amino]-N,N,N-trimethyl-, iodide (9CI)

[0129] 1-propanaminium,3-[(8-chloro-2,2,3,3,4,4,5,5,6,6,7,7,8,8-tetradecafluoro-1-oxooctyl)amino]-N,N,N-trimethyl-,methyl sulfate (9CI)

[0130] Silicone-based surfactants include: 1-propanaminium,N,N,N-trimethyl-3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]-,bromide (9CI)

[0131] Fatty zwitterionic surfactants include: 1-dodecanaminium,N-(2-hydroxy-3-sulfopropyl)-N,N-dimethyl-, inner salt (9CI)

[0132] Fatty amine oxides such as hexadecyldimethylamine oxide areincluded. Fatty anionic surfactants include: Sodium oleyl sulfate;potassium oleate; sodium dodecylbenzenesulfonate; sodium tetradecylsulfate; and disodium 2-hexadecenylbutanedioate.

Surfactants

[0133] Surfactants are an optional ingredient in some embodiments of thepresent invention. Surfactants are especially useful in the rinse aidsurface coating composition as wetting agents to facilitate thedispersion of nanoparticles onto a dishware surface. Surfactants arealternatively included when the rinse aid surface coating composition isused to treat a hydrophobic dishware surface or when the rinse aidsurface coating composition is applied with a spray dispenser in orderto enhance the spray characteristics of the rinse aid surface coatingcomposition and allow the rinse aid surface coating composition,including the nanoparticles, to distribute more evenly. The spreading ofthe rinse aid surface coating composition can also allow it to dryfaster, so that the treated material is ready to use sooner. Forconcentrated compositions, the surfactant can facilitate the dispersionof many adjunct ingredients such as dispersive polymers, pH-adjustingagents and perfumes in the concentrated aqueous compositions.

[0134] Suitable surfactants can be selected from the group includinganionic surfactants, cationic surfactants, nonionic surfactants,amphoteric surfactants, ampholytic, zwitterionic surfactants, andmixtures thereof. Examples of suitable nonionic, anionic, cationic,ampholytic, zwitterionic and semi-polar nonionic surfactants aredisclosed in U.S. Pat. Nos. 5,707,950 and 5,576,282. Nonionicsurfactants may be characterized by an HLB (hydrophilic-lipophilicbalance) of from 5 to 20, alternatively from 6 to 15.

[0135] When a surfactant is used in the rinse aid surface coatingcomposition, it may be added at an effective amount to provide one, ormore of the benefits described herein. Typically, surfactants can beincluded in an amount from about 0.01% to about 15% by weight of thecomposition, or any amount or range within this range, including, butnot limited to from about 0.01% to about 5%, 0.01% to about 3%, fromabout 0.01% to about 0.5%, however, any amount of surfactant can beused.

[0136] An alternative type of surfactant is ethoxylated surfactant, suchas addition products of ethylene oxide with fatty alcohols, fatty acids,fatty amines, etc. Optionally, addition products of mixtures of ethyleneoxide and propylene oxide with fatty alcohols, fatty acids, and fattyamines can be used. The ethoxylated surfactant includes compounds havingthe general formula:

R⁸—Z—(CH₂CH₂O)_(s)B

[0137] wherein R⁸ is an alkyl group or an alkyl aryl group, selectedfrom the group consisting of primary, secondary and branched chain alkylhydrocarbyl groups, primary, secondary and branched chain alkenylhydrocarbyl groups, and/or primary, secondary and branched chainalkyl-and alkenyl-substituted phenolic hydrocarbyl groups having fromabout 1 to about 20 carbon atoms, alternatively from about 8 to about18, alternatively from about 10 to about 15 carbon atoms; s is aninteger from about 2 to about 45, alternatively from about 2 to about20, alternatively from about 2 to about 15; B is a hydrogen, acarboxylate group, or a sulfate group, or a lower alkyl group, or a C₃and above hydroxyalkyl group; and linking group Z is —O—, —C(O)O—, or—C(O)N(R)—, and mixtures thereof, in which R, when present, is R⁸ orhydrogen.

[0138] Another class of alternative surfactants that are useful in theformulation of the rinse aid surface coating compositions are siliconesurfactants, also known as silicone superwetting agents. They can beused alone and/or alternatively in combination with the alternativealkyl ethoxylate surfactants described herein above. Non-limitingexamples of silicone surfactants are the polyalkylene oxidepolysiloxanes having a dimethyl polysiloxane hydrophobic moiety and oneor more hydrophilic polyalkylene oxide side chains, and having thegeneral formula:

R¹—(CH₃)₂SiO—[(CH₃)₂SiO]_(a)—[(CH₃)(R¹)SiO]_(b)—Si(CH₃)₂—R¹

[0139] wherein a+b are from about 1 to about 50alternatively, and eachR¹ is the same or different and is selected from the group consisting ofmethyl and a poly(ethyleneoxide/propyleneoxide) copolymer group havingthe general formula:

—(CH₂)_(n)O(C₂H₄O)_(c)(C₃H₆O)_(d)R²

[0140] wherein n is 3 or 4; total c (for all polyalkyleneoxy sidegroups) has a value of from 1 to about 100, alternatively from about 6to about 100; total d is from 0 to about 14; alternatively d is 0; totalc+d has a value of from about 5 to about 150, alternatively from about 9to about 100 and each R² is the same or different and is selected fromthe group consisting of hydrogen, an alkyl having 1 to 4 carbon atoms,and an acetyl group, alternatively hydrogen and methyl group. Eachpolyalkylene oxide polysiloxane has at least one R¹ group being apoly(ethyleneoxide/propyleneoxide) copolymer group. Siliconesuperwetting agents are available from Dow Corning as silicone glycolcopolymers (e.g. Q2-5211 and Q2-5212).

[0141] The surfactant is preferably formulated to be compatible with thenanoparticle system, the carrier medium and any optional adjunctingredients present in the rinse aid surface coating composition. Forthe rinse aid surface coating compositions, this may mean that thesurfactants are of type that (as opposed to detersive surfactants) islow sudsing and low foaming (since it is generally undesirable for thecoating to have suds or foam therein). Low foaming nonionic surfactantscan be described in terms of their cloud point. Low foaming nonionicsurfactants typically have a cloud point below 30° C. Non-limitingdescriptions of low cloud point nonionic surfactants includeC_(9/11),EO₈-cyclohexyl acetal alkyl capped nonionic, C₁₁EO₇-n-butylacetal, C_(9/11)EO₈-2-ethylhexyl acetal, C₁₁EO₈-pyranyl, alcoholalkoxylate, and mixtures thereof. More low cloud point nonionicsurfactants are described in U.S. Pat. Nos. 6,013,613 and 6,034,044.Amphoteric and anionic surfactants can be considered to be low sudsingand low foaming if they are present below a Kraft Temperature of 30° C.

Other Optional Ingredients

[0142] The rinse aid surface coating compositions can contain otheroptional ingredients, including but not limited to alkalinity sources,anti-corrosion agents, anti-microbial preservatives, antioxidants,anti-static agents, anti-tarnish agents, bleaches, bleach activators,bleach catalysts, bluing agents, builders, carriers, chelating agents,aminocarboxylate chelators, colorants, color speckles, conditioners,hydrolyzable cosurfactants, dyes, dye transfer agents, dispersants,enzymes, non-activated enzymes, enzyme stabilizing systems, fillersalts, fluorescers, fungicides, germicides, hydrotropes, metallic salts,photoactive inorganic metal oxides, photoactive nanoparticles, organicsolvents, odor-controlling materials, optical brighteners, soil releasepolymers, perfumes, photoactivators, polymers, preservatives, processingaids, pigments, and pH control agents as described in U.S. Pat. Nos.5,705,464; 5,710,115; 5,698,504; 5,695,679; 5,686,014; 5,576,282; and5,646,101, silvercare agents, solubilizing agents, suds suppressors,surfactants, water-soluble bicarbonate salts, wetting agents, Uwabsorbers, zeolites, and mixtures thereof. These optional ingredientsmay be included at any desired level.

II. METHODS OF USE

[0143] The rinse aid surface coating composition contains a nanoparticlesystem with an effective amount of non-photoactive nanoparticles in anaqueous suitable carrier medium, and optionally a dispersant polymer, asurfactant, a pH-adjusting agent, one or more charged functionalizedsurface molecules, and adjunct ingredients. The rinse aid surfacecoating compositions can be used by (a) mixing said nanoparticles insuitable carrier medium to form said surface coating composition; (b)mixing said nanoparticles dispersed in suitable carrier medium with adispersant polymer to inhibit gel formation; (c) optionally mixing saidnanoparticles dispersed in suitable carrier medium with a dispersantpolymer and adjunct ingredients to form said surface coatingcomposition; (d) optionally mixing said nanoparticles dispersed insuitable carrier medium with a dispersant polymer and a surfactant toform said surface coating composition; (e) optionally mixing saidnanoparticles dispersed in suitable carrier medium with a dispersantpolymer and a pH-adjusting agent to form said surface coatingcomposition; (f) optionally mixing said nanoparticles dispersed insuitable carrier medium with a dispersant polymer, a surfactant andadjunct ingredients to form said surface coating composition; (g)optionally mixing said nanoparticles dispersed in suitable carriermedium with a dispersant polymer, a surfactant, a pH-adjusting agent andadjunct ingredients to form said surface coating composition; (h)applying said surface coating composition to a dishware surface; (i)allowing said surface coating composition to dry, or drying the rinseaid surface coating composition; and (j) optionally repeating any ofsteps (a) through (i) as needed. In some embodiments, it may bedesirable for step (i) to be carried out without rinsing or agitatingthe rinse aid surface coating composition during drying.

[0144] The methods of use can comprise any of the following non-limitingmethods: methods of forming a substantially clear coating; methods ofproviding a dishware surface with multiple benefits; methods ofproviding a dishware surface with improved wetting and sheetingproperties; methods of providing a dishware surface with improveduniform drying properties; methods of providing a dishware surface withimproved anti-spotting properties; methods of providing a dishwaresurface with improved self cleaning properties; and methods of providinga dishware surface with improved durability properties; methods ofproviding a dishware surface with improved stain removal; methods forproviding a dishware surface with anti-stain deposition propertiesand/or cleaner appearance; methods for forming a protective coating on adishware surface; methods for cleaning a dishware surface; methods formodifying a dishware surface to increase the receptivity of the dishwaresurface to the subsequent application of a substance; methods forproviding a dishware surface with multi-use properties; and combinationsof these and other methods.

[0145] Distribution of the rinse aid surface coating composition can beachieved by using a spray device, an immersion container, a spray hoseattachment, or an applicator, such as a fabric, a porous article such asa sponge, or roller, a pad, etc., alternatively, an automaticdishwashing appliance spray dispenser or a spray dispenser. The rinseaid surface coating compositions and articles of the present inventionwhich contain the nanoparticle system can be used to treat all dishwaresurfaces to provide at least one of the following improved durable orprotective benefits: improved wetting and sheeting, uniform drying,anti-spotting, anti-staining, anti-filming, self cleaning, anddurability.

[0146] The rinse aid surface coating compositions can reduce oreliminate the formation of water beads on treated dishware surfaces thatmay be contacted with water, such as wash water or rinse water. In thecase of glass dishware, and the like, the reduction in the formation ofwater beads can improve visibility through the glassware when they arewetted by wash or rinse water. The rinse aid surface coatingcompositions can also avoid the formation of water spots left when suchwater beads dry, and any damage to the dishware surface, such as hardwater scaling. The rinse aid surface coating compositions can, in someaspects, reduce or eliminate the need to dry the dishware surface towhich it has been applied after wetted by wash or rinse water.

[0147] In one aspect of the present invention, an effective amount ofthe liquid coating composition of the present invention may bealternatively sprayed onto dishware surfaces. When the rinse aid surfacecoating composition may be sprayed onto a dishware surface, an effectiveamount of the nanoparticle system should be deposited onto the dishwaresurface, with the dishware surface becoming damp or totally saturatedwith the rinse aid surface coating composition. The rinse aid surfacecoating composition can also be applied to a dishware surface via rollcoating, curtain coating, a dipping and/or soaking process in animmersion container. Any of the application steps can be followed by adrying, or curing step.

[0148] The coating composition forms a surface coating that at leastpartially covers the dishware surface. The coating is comprised of aplurality of nonphotoactive nanoparticles which are present in an amountless than from about 3 mg/cm² of the area of the dishware surface. Notto be limited by theory, the coating may also be comprised of aplurality of nonphotoactive nanoparticles which are present in an amountless than from about 3 μg/ cm² of area of the surface. In certainembodiments, if the coating comprises a binder material, the amount ofbinder material in the coating may be less than a functional level ofbinder material. In certain embodiments, if the coating comprises apeptizer, the amount of peptizer may be less than 3%. In certainembodiments, the coating may consist essentially of nanoparticles, awetting agent, and water which forms a dry surface coating on thedishware surface being less than 300 nm thick, wherein said dry surfacecoating contains less than 4% water. The steps in some representative,but non-limiting examples of the application process are described ingreater detail below.

[0149] In one non-limiting aspect of the present invention, the rinseaid surface coating composition may be used to apply a durable,protective coating on the surface of dishware. The steps in applying therinse aid surface coating composition can involve one or more of thefollowing steps, in addition to a step of applying the rinse aid surfacecoating composition: a pre-treatment; a pre-wash step; a washing step,such as with soap and a sponge to produce lather; a rinse step; anactivated rinse step; a step for applying the rinse aid surface coatingcomposition described herein; and a drying step. These steps can beperformed by consumers at home, such as if they are provided with thecomponents needed to carry out the steps in the form of a kit, such as adishcare kit. Instructions can be provided. Alternatively, the steps canbe performed in a commercial operation, such as at a dishwaremanufacturing facility. These steps can be adapted to apply the coatingcomposition to any other types of dishware surfaces.

Applying a Rinse Aid Surface Coating Composition ComprisingNon-Photoactive Nanoparticles to a Dishware Surface

[0150] The rinse aid surface coating composition comprising thenon-photoactive nanoparticles is applied to the dishware surface. Thedishware surface should preferably be as clean as possible, althoughcleaning is not a required step in applying the rinse aid surfacecoating composition. The rinse aid surface coating composition can beapplied to the dishware surface while the dishware surface is still wetfrom washing with tap water, or when the dishware surface of thedishware surface is dry. The rinse aid surface coating composition canbe applied to the dishware surface in any suitable manner including, butnot limited to pouring, wiping (such as with a sponge, cloth, or thelike), and spraying.

[0151] In embodiments using aqueous liquid rinse aid surface coatingcompositions comprising non-photoactive nanoparticles, the compositionshould first be shaken to ensure that the nanoparticles are adequatelydispersed in the solution before it is applied to the dishware surface.

[0152] It has been found that the properties of the rinse aid surfacecoating composition and the manner of applying the rinse aid surfacecoating composition can have a considerable impact on the finalappearance of the coated dishware surface, particularly high glossdishware surfaces, such as plastic, glass or ceramic dishware surfaces.It is not trivial to deliver a residue-free nanoparticle coating thatprovides the desired hydrophilic dishware surface modification. Forexample, the manner and amount of the rinse aid surface coatingcomposition that is applied can have a significant impact on the finalappearance of the dishware surface. It is, therefore, desirable todevelop a rinse aid surface coating composition that is not overlysensitive to the environmental conditions of the automatic dishwashingappliance, and to apply the rinse aid surface coating composition in amanner that forms a residue-free nanoparticle coating that provides thedesired hydrophilic dishware surface modification.

[0153] It has been found that when the rinse aid surface coatingcomposition comprises LAPONITE B™ nanoparticles, it is capable ofproviding a more uniform rinse aid surface coating in glass (that is,more continuous, i.e., less openings in the way the rinse aid surfacecoating forms after drying), and can provide a more substantive (ordurable) rinse aid surface coating than some of the other grades ofLAPONITE by themselves (such as LAPONITE RD™). The rinse aid surfacecoating preferably forms at least one layer of nanoparticles on thedishware surface which has been coated, and is substantially uniform.

[0154] Conversely, it has been found that when the rinse aid surfacecoating composition comprises LAPONITE RD™ nanoparticles, it is capableof providing a more uniform rinse aid surface coating on plastic (thatis, more continuous, i.e., less openings in the way the rinse aidsurface coating forms after drying), and can provide a more substantive(or durable) rinse aid surface coating than some of the other grades ofLAPONITE™ by themselves (such as LAPONITE B™). See FIGS. 4a-d.

[0155] It has also been found that when the rinse aid surface coatingcomposition comprises certain surfactants, a more suitable rinse aidsurface coating is formed than when using other surfactants. The rinseaid surface coating formed thereby is much less effected by thesubsequent wash conditions. The use of the preferred types ofsurfactants described herein, such as MIN-FOAM™ surfactant, alsoprovides a suitable dishware surface coating using a much lesser amountof non-photoactive nanoparticles, as well as a lesser amount of thesurfactant. The reduction in the amount of non-photoactive nanoparticlesmay approach one-half of the amount of non-photoactive nanoparticlesthat must be used with other types of surfactants. The MIN-FOAM™surfactant uses up to 15% less surfactant to deliver the LAPONITE B™ tothe dishware surface. Without wishing to be bound to any particulartheory, this is believed to be due to the low critical micelleconcentration (CMC) of the MIN-FOAMM surfactant. Additionally, theMIN-FOAM™ surfactant produces less visible residue due to lower sudsgenerating when the composition is delivered to the substrate using asprayer. However, certain types of sprayers, including, but not limitedto electrostatic sprayers, may cause fewer suds or bubbles to beintroduced into the rinse aid surface coating composition duringapplication to the dishware surface, which form suitable rinse aidsurface coatings with less visible residue under a wider variety ofconditions.

[0156] In one non-limiting embodiment, the rinse aid surface coatingcomposition is applied to the dishware surface during one or more cyclesin an automatic dishwashing appliance. The rinse aid surface coatingcomposition may be sprayed onto the dishware surface of the dishware atany flow rate provided during the wash and/or rinse cycles of a standardautomatic dishwashing appliance. Furthermore, this applies to flow ratesprovided by commercial applications as well.

[0157] In one non-limiting embodiment, the rinse aid surface coatingcomposition is applied directly to the dishware surface using a cloth,sponge, or foam squeegee. A rinse aid surface coating compositioncomprising about 0.055% of nanoparticles can be applied directly to thedishware surface of the dishware in this manner.

[0158] In another non-limiting embodiment, the rinse aid surface coatingcomposition is sprayed onto the dishware surface of the dishware. Therinse aid surface coating composition may be sprayed onto the dishwaresurface of the dishware at a flow rate that is less than or equal toabout 8 gal./min. (about 30 L/min) for hose-end type sprayers, or anyflow rate less than that flow rate and all such spray rates, including,but not limited to less than or equal to about 0.1 gal./min. (about 0.38L/min.), or less than or equal to about 0.05 gal./min. (about 0.19L/min.) are incorporated herein.

Forming A Wet Surface Coating of Nanoparticles

[0159] The preceding step preferably forms a substantially aqueousuniform wet surface coating comprising a plurality of nanoparticles, onthe dishware surface. Uniform coverage of the dishware surface isdesired in order to provide the benefits described herein to the entiredishware surface to be treated.

[0160] The wet surface coating should be capable of drying to a drystate. Between the wet state and the dry state, the rinse aid surfacecoating will typically pass through various partially dried states. Inorder to form a dry surface coating that has the desired uniformcharacteristics described herein, the wet surface coating should be asfree as possible from coating imperfection-producing substances.Therefore, a step in the process may include at least partially removingimperfection-producing substances from the dishware surface to be coatedand from the wet surface coating. Such imperfection-producing substancesmay include, but are not limited to deposits which can be left by tapwater, air bubbles, etc. The wet surface coating should preferably bespread uniformly across the dishware surface, and preferably should notdevelop breaks in the uniformity during the drying process.

[0161] Air bubbles in the wet surface coating can, in certaincircumstances, cause serious defects in the finally-formed dry surfacecoating. In certain embodiments, it is desirable for the wet surfacecoating to have less than 61 (or less than or equal to 60) defects thatare greater than or equal to 1.75 mm in width per 100 cm² of thedishware surface as measured at any time more than 30 seconds after thewet surface coating is formed on the dishware surface. If the airbubbles are of a relatively small size (e.g., in some cases having amean size less than or equal to about 4 mm (e.g. 3.75mm)) or there are alimited number of bubbles of a size greater than or equal to about 1.75mm, or if they break while the wet surface coating is still in apartially dried state, this can minimize defects in the dry surfacecoating. When air bubbles break when the wet surface coating is still ina sufficiently early partially dried state, the adjacent portions of thewet surface coating can flow into the openings created when the airbubbles break, and fill the same to eliminate any gaps in the drysurface coating. Therefore, the wet surface coating is preferablysubstantially free of air bubbles that break after the wet surfacecoating is in a partially dried state. For this reason, it is desirable,when spraying the rinse aid surface coating composition on the dishwaresurfaces, to select a type of sprayer that will minimize the quantityand size of air bubbles in the wet surface coating.

Allowing the Surface Coating Composition to Dry on the Dishware SurfaceBefore the Dishware Surface is Contacted by Water to Form a Dry SurfaceCoating on the Dishware Surface

[0162] The dishware surface with the wet surface coating of the rinseaid composition thereon should preferably be allowed to dry. Thedishware surface should be allowed to dry without agitation, scrubbing,or otherwise disturbing the treated dishware surface (that is, the wetsurface coating). In certain embodiments, the wet surface coating shouldbe allowed to dry for at least about 15 minutes, preferably at leastabout one-half hour, more preferably at least about 2 hours, morepreferably still at least about 4 hours, and most preferably up to about24 hours before any water contacts the treated dishware surface.

[0163] After drying, the surface coating composition forms a dry surfacecoating on the dishware surface. The surface coating composition atleast partially covers the dishware surface. The surface coatingcomposition preferably forms a dry surface coating comprising at leastone layer of nanoparticles on the dishware surface which has beencoated, and is substantially uniform. In certain embodiments, the drysurface coating comprises primarily (or alternatively, consistsessentially of) nanoparticles, and some remaining amounts of water and,in some cases, a wetting agent or surfactant. The dry surface coatingcan have any suitable amount of nanoparticles therein. Preferably, thedry surface coating has a sufficient amount of nanoparticles to providethe dishware surface of the dishware with the desired hydrophilicity.Preferably, the dry surface coating comprises non-photoactivenanoparticles in an amount greater than or equal to about 0.2 μg/cm² ofthe dishware surface area treated. In certain embodiments, the drysurface coating comprises less than 3 μg/cm² of non-photoactivenanoparticles relative to the area of the dishware surface treated for aresidue-free appearance. In certain embodiments, if the rinse aidsurface coating composition comprises other materials, such as a bindermaterial, the amount of binder material in the dry surface coating maybe less than a functional level of binder material. In certainembodiments, if the rinse aid surface coating composition comprises apeptizer, the amount of peptizer may be less than 3%. The term“peptizer”, as used herein, includes, but is not limited to sodiumtripolyphosphate, sodium orthophosphate, tetrasodium pyrophosphate. Thedry surface coating can provide the composite dishware surface (orcoated dishware surface) with any suitable degree of hydrophilicitydescribed herein. In preferred embodiments, the contact angle ofdistilled water on the dry surface coating is less than or equal toabout 50°, or less than or equal to any number of degrees less than 50°(including, but not limited to less than, or less than or equal to,about 35°, 25°, 20°, 15°, etc.).

[0164] It is often desirable for the dry surface coating to be asdefect-free as possible. In certain embodiments, the dry surface coatingmay have visual scores under the Visual Grading Test in the Test Methodssection of greater than or equal to −2. Preferably, the dry surfacecoating has a thickness of less than, or less than or equal to, about400 nm, or less than, or less than or equal to, any number of nanometersless than 400, including, but not limited to 300, 200, etc. The thinnerdry surface coatings will typically have better transparency.

[0165] In certain non-limiting embodiments, the rinse aid surfacecoating composition enhances the gloss of dishware surfaces that areinitially dull, preferably by at least about 10%. In the case ofdishware surfaces that have a high initial gloss, in certainembodiments, the rinse aid surface coating composition may eithermaintain or enhance the initial gloss, or does not cause more than a 10%reduction in the gloss. For example, dishware surfaces with an initialgloss reading at 60° geometry of greater than or equal to 10 arepreferably treated with a rinse aid surface coating composition whichresults in less than 10% reduction of specular gloss value aftertreatment. Dishware surfaces with an initial gloss reading at 60°geometry of less than 10 are preferably treated with a rinse aid surfacecoating composition which results in greater than 10% increase ofspecular gloss value after treatment.

Increasing the Durability of the Surface Coating

[0166] The rinse aid surface coating composition can be applied to thedishware surface at any suitable air temperature. It has been found thatthe rinse aid surface coating composition can be applied at anytemperature above freezing. For instance, the rinse aid surface coatingcomposition can be applied at temperatures as low as 1°, 5°, 10°, or 15°C.

[0167] The dishware surface can then be subjected to conditions so as toremove water from, cure or otherwise dry the rinse aid surface coatingcomposition. The drying step can comprise air drying in ambientconditions. Alternatively, the drying step can comprise actively dryingor curing the rinse aid surface coating composition by utilizing anytechnology known for accelerating a drying or curing process. The term“actively curing”, as used herein, refers to any technique used toaccelerate the curing process beyond merely allowing the rinse aidsurface coating composition to dry under ambient conditions. Forinstance, known cross-linking agents can be incorporated into thecomposition to cure the same. Although various methods of curing may beused, thermal or heat curing, or heat drying is preferred. The rinse aidsurface coating composition can be heat dried at any air temperaturewhich is above the ambient temperature (which air temperature of dryingmay, for example, be greater than or equal to about any five degreeincrement above 0° C.). Generally, heat curing is effected by exposingthe coated dishware surface to elevated temperatures, such as thosewhich are provided by the radiative heat sources in automaticdishwashing appliances. Such technology may include moving (or forced)air drying such as drying by fans, blow drying, etc., or the applicationof heat (such as by radiative heat sources, such as drying in ovens,etc.), or both moving or forced air drying and the application of heat(such as heated blow drying). Alternatively, the water content of therinse aid surface coating can be achieved by reducing the vapor pressureabove the rinse aid surface coating using vacuum methods.

[0168] It has been found that reducing the water content of the rinseaid surface coating composition can greatly increase the durability ofthe dishware surface coating. In certain embodiments, it may bedesirable for the water content to be less than or equal to, or lessthan, about 4% (or any whole number, decimal, or number containing afraction which is less than 4, all of which numbers are incorporatedherein). The amount of increase in the durability of the dishwaresurface coating can, in fact, be quite unexpectedly high.

[0169] For instance, in some embodiments, it has been found that whenthe rinse aid surface coating composition may be applied to the dishwaresurface and air dried at ambient temperature, the dishware surfacecoating may be able to provide the benefits described herein (or atleast some of such benefits) after it has been subjected to one or tworoutines/cycles of the mechanical scrub method described in the testmethods section below. This is believed to translate into about two tofour weeks of dishware surface protection and modification in anautomatic dishwasher environment, including washing the dishware surfaceabout twice a week.

[0170] However, if the rinse aid surface coating composition may be heatdried above ambient temperature, the dishware surface coating formed onthe dishware surface has been found to have increased durability, sothat it provides more lasting benefits. The term “long lasting”, as usedherein, refers to a rinse aid surface coating that may be able toprovide at least some of the benefits described herein after more thanone cycle of the Scrub Method described in the Test Methods section. Therinse aid surface coating composition can be heat dried at any airtemperature of greater than or equal to about 50° C. and any five degreeincrement above 50° C. (e.g., 80° C., 100° C., 120° C., etc.; alltemperatures in five degree increments are incorporated herein) toprovide long lasting benefits. However, this could be influenced byaccelerants, i.e., solvents and cross-linking agents. The rinse aidsurface coating composition can be dried for any suitable amount of timegreater than or equal to a flash, or greater than, 1 minute, or anynumber of minutes greater than 1 minute (including, but not limited to 5minutes and 10 minutes). The rinse aid surface coating composition canbe air dried at temperatures that approach, but alternatively do notexceed a temperature that would cause the dishware surface being coatedto be altered, such as by melting, buckling, or the like. In onenon-limiting embodiment, the rinse aid surface coating composition canbe applied to dishware, and then heat dried at an air temperature ofabout 145° C. to about 160° C., or any five degree incrementtherebetween. It has been found that a rinse aid surface coating driedwith such a heat drying process can withstand 500 or more cycles of themechanical scrubbing test. In another non-limiting embodiment, the rinseaid surface coating composition can be applied to a dishware article,and then heat dried at an air temperature of about 135° C. It has beenfound that a rinse aid surface coating dried with such a heat dryingprocess can withstand 50 or more cycles of the mechanical scrubbingtest.

[0171] In another non-limiting embodiment, the rinse aid surface coatingcomposition can be applied to dishware, and then heat dried at an airtemperature of about 135° C. It has been found that a rinse aid surfacecoating dried with such a heat drying process can withstand 50 or morecycles of the mechanical scrubbing test.

[0172] The dried dishware surface coating may be alternativelysubstantially hydrophilic. The dried dishware surface, in someembodiments may have a contact angle with water of: less than or equalto about 60; or alternatively, less than or equal to about any incrementof five less than 60 (e.g., less than or equal to about 50, 45, 40, . .. , 20, . . . , 10, etc.). In some embodiments, higher temperatures ofapplication or drying result in higher initial contact angles, and lowertemperatures of application or drying result in lower initial contactangles. However, the contact angle can change over the duration of thecoating. The visual appearance of the dried hard surface coating afterwetting, in some embodiments, can be improved after the surface is firsthydrated for 500 seconds. The visual improvement is characterized asimproved sheeting or improved curtaining of water on the surfacecoating.

[0173] In other embodiments, it may be desired to use nanoparticles inthe form of a powder. The nanoparticles can be used alone, or they canbe combined with some other substance to form a clear coatingcomposition. The clear coat composition, in such embodiments can beprovided in any suitable form, including, but not limited to liquids,and powders. In embodiments in which it may be desired to use a powderdishware surface coating comprising nanoclay with a powder clear coat,it may be desirable to modify the application procedure. The applicationprocedure can be modified in many different ways. In any embodimentsdesired, the dishware surface onto which the powder coating may bedeposited can also be charged to facilitate attraction and adherence ofthe nanoparticles thereto.

[0174] For instance, in certain metal dishware the clear coat powdercomposition can first be applied by electrostatic deposition techniquesor fluidized bed techniques or other such techniques that may becommonly practiced, followed by application of the nanoclay rinse aidsurface coating composition by electrostatic deposition or fluidized bedor other such techniques that may be commonly practiced. The metaldishware surface can then be heated to provide adequate curing.

[0175] In another embodiment, the metal dishware surface can first becoated with the powdered rinse aid surface coating compositioncomprising nanoclay. This can be followed by application of a clear coatpowder composition by electrostatic deposition techniques or fluidizedbed techniques or other such techniques that may be commonly practiced.The metal dishware surface can then be heated to provide adequatecuring.

[0176] In another embodiments, the clear coat powder composition and therinse aid surface coating composition comprising nanoclay can be appliedsimultaneously to the desired metal dishware surface by electrostaticdeposition techniques or fluidized bed techniques or other suchtechniques that may be commonly practiced. The metal dishware surfacecan then be heated to provide adequate curing.

[0177] In any of the embodiments described in this specification,multiple layers of the rinse aid surface coating composition can beapplied to any of the dishware surfaces described herein. These multiplelayers of rinse aid surface coating composition can all have the samechemical composition, or they can have different chemical compositions.

[0178] The present invention also comprises a method of usingconcentrated liquid or solid coating compositions, which may be dilutedto form compositions with the usage concentrations, as givenhereinabove, for use in the “usage conditions”. Concentratedcompositions comprise a higher level of nanoparticle concentration,typically from about 0.1% to about 50%, alternatively from about 0.5% toabout 40%, alternatively from about 1% to about 30%, by weight of theconcentrated coating composition.

[0179] Concentrated compositions may be used in order to provide a lessexpensive product. The concentrated product may be alternatively dilutedwith 1,000 parts suitable carrier medium, alternatively 100 partssuitable carrier medium, and alternatively 10 parts suitable carriermedium of the rinse aid surface coating composition.

[0180] In another embodiment of the present invention there may be aprovided a method of using a liquid, coating composition comprising (a)an effective amount of non-photoactive nanoparticles; (b) optionally asurfactant; (c) optionally having associated to said nanoparticlesurface a quantity of one or more functionalized surface moleculesexhibiting properties selected from the group consisting of hydrophilic,hydrophobic and mixtures thereof; (d) optionally an effective amount ofphotoactive nanoparticles; (e) optionally one or more adjunctingredients; and (f) a suitable carrier medium, alternativelyconcentrated liquid, for treating dishware in the rinse step of anautomatic dishwashing appliance. The rinse water should containtypically from about 0.0005% to about 1%, alternatively from about0.0008% to about 0.1%, alternatively from about 0.001% to about 0.02% ofthe nanoparticle.

[0181] Another alternative method comprises the treatment of dishwarewith a rinse aid surface coating composition dispensed from a sprayer atthe beginning and/or during the drying cycle. It may be preferable thatthe treatment is performed in accordance with the instructions for use,to ensure that the consumer knows what benefits can be achieved, and howbest to obtain these benefits.

[0182] Another alternative method comprises stripping at least one layerof nanoparticles from the transparent coating on a treated dishwaresurface using mechanical or chemical means to remove the layer offoreign matter (i.e. stain, spotting residues, food etc.) in accordancewith the instructions for use to impart the benefits desired, whereinmechanical or chemical means does not exclude the weathering oroptionally the normal use of the dishware surface. Not to be limited bytheory, the strippable-coating mechanism of this method is depicted inFIGS. 1-3.

[0183] In FIGS. 1-3, the dishware surface may be designated by referencenumber 20. The individual nanoparticles may be designated by referencenumber 22, and the layers formed thereby may be designated by referencenumber 24. The stain deposited on the nanoparticles may be designated byreference number 26. In one embodiment of the present invention, such asdishware surface application, an effective nanoparticle coating may bedeposited as an invisible coating, preventing stain 26 from adhering tothe dishware surface 20 (FIG. 1). The nanoparticle coating consists ofmultiple effective layers 24 of nanoparticle sheets that provide thebenefit. During the washing or stripping treatment process, at least onetop layer 24 of the nanoparticle coating may be removed, taking thestain 26 along with it (FIGS. 2 and 3).

III. ARTICLES OF MANUFACTURE

[0184] The present invention also relates to an article of manufacturecomprising the rinse aid surface coating composition in a package, inassociation with instructions for how to use the rinse aid surfacecoating composition to treat dishware surfaces correctly, in order toobtain the desirable results described herein. An alternative article ofmanufacture comprises said composition in an automatic dishwashingappliance spray dispenser or a spray dispenser in association withinstructions for how to use the rinse aid surface coating composition totreat dishware surfaces correctly, including, e.g., the manner and/oramount of composition to spray, and the alternative ways of applying therinse aid surface coating composition. It may be important that theinstructions be as simple and clear as possible, so that using picturesand/or icons may be desirable.

Spray Dispenser

[0185] The rinse aid surface coating composition may be placed into aspray dispenser in order to be distributed onto the dishware surface.The spray dispenser can be any of the manually activated types forapplying the coating composition to small dishware surface areas and/ora small number of substrates, as well as non-manually operated, poweredsprayers for conveniently applying the coating composition to largedishware surface areas and/or a large number of substrates. The spraydispenser can include, but are not limited to any of the following:aerosol spray dispensers, self-pressurized spray dispensers,non-aerosol, manually activated, pump-spray dispensers,manually-activated trigger-spray dispensers, trigger sprayers or fingerpump sprayers, non-manually operated spray dispensers including, but notlimited to, powered sprayers, air aspirated sprayers, liquid aspiratedsprayers, electrostatic sprayers, and nebulizer sprayers. Poweredsprayers can include, but are not limited to, centrifugal or positivedisplacement designs. Powered sprayers are readily available fromsuppliers such as Solo, Newport News, Va. (e.g., Solo Spraystar™rechargeable sprayer, listed as manual part #: US 460 395). Certaintypes of sprayers, including, but not limited to electrostatic sprayers,may cause fewer suds or bubbles to be introduced into the treatingcomposition during application to the dishware surface, which formsuitable coatings with less visible residue under a wider variety ofconditions. This may allow a wider range of surfactants to be used inthe coating composition.

[0186] It is preferred that the powered sprayer be powered by a portableDC electrical current from either disposable batteries (such ascommercially available alkaline batteries) or rechargeable battery units(such as commercially available nickel cadmium battery units). Poweredsprayers can also be powered by standard AC power supply available inmost buildings. The discharge nozzle design can be varied to createspecific spray characteristics (such as spray diameter and particlesize). It is also possible to have multiple spray nozzles for differentspray characteristics. The nozzle may or may not contain an adjustablenozzle shroud that would allow the spray characteristics to be altered.Electrostatic sprayers impart energy to the aqueous coating compositionvia a high electrical potential. This energy serves to atomize andcharge the aqueous coating composition, creating a spray of fine,charged particles. As the charged particles are carried away from thesprayer, their common charge causes them to repel one another. This hastwo effects before the spray reaches the target. First, it expands thetotal spray mist. This is especially important when spraying to fairlydistant, large areas. The second effect is maintenance of originalparticle size. Because the particles repel one another, they resistcollecting together into large, heavier particles like unchargedparticles do. This lessens gravity's influence, and increases thecharged particle reaching the target. As the mass of negatively chargedparticles approach the target, they push electrons inside the targetinwardly, leaving all the exposed surfaces of the target with atemporary positive charge. The resulting attraction between theparticles and the target overrides the influences of gravity andinertia. As each particle deposits on the target, that spot on thetarget becomes neutralized and no longer attractive. Therefore, the nextfree particle is attracted to the spot immediately adjacent and thesequence continues until the entire surface of the target is covered.Hence, charged particles improve distribution and reduce drippage.

[0187] Non-limiting examples of commercially available electrostaticsprayers appears in U.S. Pat. Nos. 5,222,664, Noakes, issued Jun. 29,1993; 4,962,885, Coffee, issued Oct. 16, 1990; 2,695,002, Miller, issuedNov. 1954; 5,405,090, Greene, issued Apr. 11, 1995; 4,752,034, Kuhn,issued Jun. 21, 1988; 2,989,241, Badger, issued Jun. 1961. Electrostaticsprayers are readily available from suppliers such as Tae In Tech Co,South Korea and Spectrum, Houston, Tex.

[0188] The article of manufacture may comprise a combination of anon-manually operated sprayer and a separate container of the rinse aidsurface coating composition, to be added to the sprayer before useand/or to be separated for filling/refilling. The separate container cancontain a usage composition, or a concentrated composition to be dilutedbefore use, and/or to be used with a diluting sprayer, such as with aliquid aspirated sprayer, as described above.

[0189] The separate container may have structure that mates with therest of the sprayer to ensure a solid fit without leakage, even aftermotion, impact, etc. and when handled by inexperienced consumers. Thesprayer desirably can also have an attachment system that is safe andalternatively designed to allow for the liquid container to be replacedby another container that is filled. For example, a filled container canreplace the fluid reservoir. This can minimize problems with filling,including minimizing leakage, if the proper mating and sealing means arepresent on both the sprayer and the container. Desirably, the sprayercan contain a shroud to ensure proper alignment and/or to permit the useof thinner walls on the replacement container. This minimizes the amountof material to be recycled and/or discarded. The package sealing ormating system can be a threaded closure (sprayer) which replaces theexisting closure on the filled and threaded container. A gasket isdesirably added to provide additional seal security and minimizeleakage. The gasket can be broken by action of the sprayer closure.These threaded sealing systems can be based on industry standards.However, it is highly desirable to use a threaded sealing system thathas non-standard dimensions to ensure that the proper sprayer/bottlecombination is always used. This helps prevent the use of fluids thatare toxic, which could then be dispensed when the sprayer is used forits intended purpose.

[0190] An alternative sealing system can be based on one or moreinterlocking lugs and channels. Such systems are commonly referred to as“bayonet” systems. Such systems can be made in a variety ofconfigurations, thus better ensuring that the proper replacement fluidis used. For convenience, the locking system can also be one thatenables the provision of a “child-proof” cap on the refill bottle. This“lock-and-key” type of system thus provides highly desirable safetyfeatures. There are a variety of ways to design such lock and keysealing systems.

[0191] Care must be taken, however, to prevent the system from makingthe filling and sealing operation too difficult. If desired, the lockand key can be integral to the sealing mechanism. However, for thepurpose of ensuring that the correct recharge or refill is used, theinterlocking pieces can be separate from the sealing system. E.g., theshroud and the container could be designed for compatibility. In thisway, the unique design of the container alone could provide therequisite assurance that the proper recharge/refill is used.

[0192] Rinse aid surface coating compositions of the present inventionfor use to treat dishware surfaces, in different steps of the automaticdishwashing processes, e.g., pre-wash, wash cycle, rinse cycle, anddrying cycle, can be packaged in association with instructions for howto use the coating composition to treat dishware correctly, in order toobtain the desired

[0193] The present invention also relates to an article of manufacturecomprising a rinse aid surface coating composition for use in sprayingand/or misting an entire dishware surface or article in a manner suchthat excessive amounts of the coating composition are prevented frombeing released to the open environment, provided in association withinstructions for use to ensure that the consumer applies at least aneffective amount of nanoparticle system and/or coating composition, toprovide the desired dishware surface multi-use benefit.

PRODUCT WITH INSTRUCTIONS FOR USE

[0194] The present invention also encompasses the inclusion ofinstructions on the use of the rinse aid surface coating compositions ofthe present invention with the packages containing the rinse aid surfacecoating compositions herein or with other forms of advertisingassociated with the sale or use of the rinse aid surface coatingcompositions for dishware. The instructions may be included in anymanner typically used by consumer product manufacturing or supplycompanies. Examples include providing instructions on a label attachedto the container holding the rinse aid surface coating composition; on asheet either attached to the container or accompanying it whenpurchased; or in advertisements, demonstrations, and/or other written ororal instructions which may be connected to the purchase or use of therinse aid surface coating compositions, including, but not limited tovideotapes and computer disks of any type.

[0195] Specifically the instructions will include a description of theuse of the rinse aid surface coating composition, for instance, therecommended amount of composition to use in order to coat the dishwaresurface or article the recommended amount of composition to apply to thedishware surface; if spraying, soaking or rubbing may be appropriate.The instructions may provide that the user is to allow the rinse aidsurface coating composition to dry without rinsing or agitating thesame.

[0196] The rinse aid surface coating compositions of the presentinvention may be alternatively included in a product. The productalternatively comprises a rinse aid surface coating composition inaccordance with the present invention, and further comprisesinstructions for using the product to treat dishware surfaces bycontacting a dishware surface in need of treatment with an effectiveamount of the rinse aid surface coating composition such that the rinseaid surface coating composition imparts one or more desired surfacecoating benefits to the dishware surface.

[0197] The compositions and methods of the present invention can be usedfor domestic modification of dishware surfaces, or for industrialmodification of dishware surfaces, such as in dishware manufacturing.

TEST METHODS

[0198] Unless otherwise stated, all tests are performed with standardautomatic dishwasher appliances. All parts, percentages and ratios usedherein are expressed as percent weight unless otherwise specified.

Procedure for Measurement of Durability of Coating

[0199] Procedure:

[0200] 1. Clean surface: Dishware may be cleaned and used as receivedwith desired coating applied. If X-ray fluorescence (XRF) analysis isperformed, dishware may be cleaned by an ethanol rinse, followed bywashing with DAWN® dishwashing liquid available from The Procter &Gamble Company of Cincinnati, Ohio, USA wash and deionized water rinseprior to use in the scrub test.

[0201] 2. Apply product with hand pump sprayer until dishware surfacemay be completely wet, allow to air dry (2 hr. minimum).

[0202] 3. Heat in oven for 25 min. (at desired temperature, e.g., one ofthe temperatures listed in Table 4), allow to cool to room temperature.

[0203] 4. Measure contact angle.

[0204] 5. Assess visual performance.

[0205] 6. Perform scrub test.

[0206] 7. Assess visual performance.

[0207] 8. Measure contact angle once dishware has dried.

[0208] 9. Perform dye or XRF analysis.

Visual Performance Assessment

[0209] The substrate may be rinsed with water, while the dishwaresurface may be held at a 90° angle to horizontal, and the dishwaresurface may be judged to determine whether it exhibits sheeting,curtaining, or beading. “Sheeting” is when an even film of water coversthe substrate, and slowly dries down without developing breaks in therinse aid surface coating. “Curtaining” occurs when the water slowlypulls into the middle and drains off the substrate. Performance may bejudged to be “beading” when the water shows no affinity for the surface,and quickly runs off the substrate.

Scrub Method for Measurement of Durability

[0210] Sheen Wet Abrasion Scrub Tester (Model 903PG, Sheen InstrumentsLtd., Kingston, England) may be fitted with 4-3.25″×1.5″×1.75″ (8.25cm×3.8 cm×4.4 cm) sponges saturated with 30 mL of 0.2% DAWN® dishwashingliquid in deionized water with 10 grains per gallon added hardness (3:1molar ratio Ca²⁺:Mg²⁺). The instrument may be set to 30 cycles perminute, with 200 g weights on each of the 300 g carrier arms for a totalof 500 g per carrier arm. Scrub levels: 0, 10, 50, 100, 500 scrubs.

Contact Angle

[0211] Deionized water (25 □L) may be pipetted onto the coatedsubstrate, and contact angle may be measured using a goniometer (NRLC.A.Model #100-00 115 from Reme-Hart Inc., Mountain Lakes, N.J., USA,with Olympus TGHM light source, Olympus Optical Co., Ltd., Japan) Threemeasurements may be made and averaged for each sample tested.

[0212] The surfaces treated by the methods and with the compositionsdescribed herein can have a lower contact angle with water than the samesurface which has not been treated as described herein.

Dye Analysis

[0213] Only white dishware surfaces can be used for this analysis. Thedishware surface may be thoroughly rinsed with a solution of thionincationic dye (500 ppm in deionized water), followed by a rinse withwater to remove excess dye. An untreated dishware surface of the sametype may be used as a control. The surface coverage of the synthetichectorite coating can be assessed qualitatively by visual evaluation orby Hunter Miniscan XE measurements.

X-Ray Fluorescence-Analysis

[0214] X-Ray Fluorescence (XRF) is a nondestructive and noninvasivetechnique that assesses the concentration of elements in a dishwaresample or on the surface of a dishware sample. The analysis may beperformed using a Phillips Analytical, 12 Michigan Dr. Natick, Mass.01760, USA, PW2404 Sequential “4000W” X-Ray Spectrometer System, SerialNo. DY735. The instrument settings and specifications for XRF analysisare set out in Table A below.

[0215] Measurement Procedure:

[0216] 1) Calibration curves that relate instrument response to analyteconcentration can be constructed by pipetting known concentrations ofstandards on the desired substrate. Standards are allowed to slowly drybefore measurements are performed.

[0217] 2) The standard or sample may be assayed by placing the sampleface down in a sample cup, loading the sample cup into the spectrometer,and initiating the data acquisition sequence. In the case of synthetichectorite coatings, the element lines for Mg and Si may be measuredwhereas the element line for Al may be used for aluminum oxide coating.

[0218] 3) Concentration for samples may be determined from thecalibration curve for standards. TABLE A General conditions used ondishware surfaces Sample Chamber Environment Vacuum Collimator mask size16 mm Collimator size 700 □m Voltage 32 kV Current 125 mA Detector typeGoniometer Analysis time 30 sec. Element line assayed Kal for desiredelement Sample Spinner On Tube Type Rhodium

Gravimetric Test for Determining Drying Time

[0219] The relative quickness of drying of a dishware surface that hasbeen wetted can be measured with and without treatment by thecompositions disclosed herein, by simple gravimetric methods. A sampleof material from which the surface is made is weighed. The sample maythen be wetted with water and allowed to dry. The sample with any waterremaining thereon may be weighed at various times throughout the dryingprocess, and plotted in the form of a graph. When drying times arecompared herein, they may be compared in terms of weight of waterremaining on the sample after a given time, which time used herein maybe ten minutes.

Procedure for Comparison of Residue Formation from Food on Surfaces

[0220] Surfaces to which this method may be applicable include, but arenot limited to, dishware, cookware, tableware including ceramic ware andglassware.

[0221] Procedure:

[0222] 1. Clean surface: Dishware samples may be used as received. Thedishware samples may be washed with surfactant solution and rinsed withdeionized water prior to use in the residue test and are cleaned byrepeatedly wiping with isopropanol and rinsing with distilled wateruntil rinse water beads or runs off tile in less than 5 seconds.

[0223] 2. If gravimetric comparison of residue is to be performed, eachsurface (e.g. each dishware sample) may be weighed before application ofthe residue solution (initial weight).

[0224] 3. Apply nanoparticle hard surface coating product with hand pumpsprayer until surface is completely wet, allow to air dry (4 hr.minimum).

[0225] 4. A residue solution, which will result in residue upon drying,may be applied with a hand pump sprayer until the dishware surface iscompletely wet. The surface may be allowed to air dry (6 hour minimum).

[0226] Analysis:

[0227] 1. Visual assessment of residue formation on the dishwaresurfaces may be performed for example by counting the number of residuespots, grading for the amount of streaking and measurement ofgloss/haze.

[0228] 2. Gravimetric comparison of residue may be performed wherepossible. Once the residue has dried completely, each dishware surfacemay be weighed (final weight) and the weight of the residue on thesurface may be determined by subtracting the initial weight of thesurface from the final weight.

Measurement of Gloss

[0229] The gloss of a surface can be measured using gloss meters andstandard optical profilimetry methods.

Procedure for the Measurement of Specular Gloss of Dishware Surfaces

[0230] Procedure:

[0231] 1. Clean dishware surface: The dishware surface to be tested iswashed with 1% DAWN® dishwashing liquid (available from The Procter &Gamble Company of Cincinnati, Ohio, U.S.A.) solution and rinsed withdeionized water prior to use.

[0232] 2. Calibrate a Photovolt “G-3” Gloss meter (BYK-Gardner USA,Rivers Park II, 9104 Guilford Road, Columbia, Md. 21046, USA.) accordingto manufacturer's instructions and measure specular gloss of the surfaceat 60° geometry. If the gloss value is lower than 10 (e.g., for dull ormatte surfaces), the 85° geometry should be used for comparisons. If thegloss value is ≧10 and <70, inclusive (medium gloss surfaces), the 60°geometry should continue to be used. If it is greater than 70 (highgloss surfaces), the 20° geometry should be used. At least 3 readingsare taken for each surface type at the applicable geometry.

[0233] 3. If a rinse aid coated surface is available, proceed to thenext step. If the dishware surface has not been coated, apply thenanoparticle solution to the dishware surface and allow the specimen toair dry in a horizontal position (4 hr. minimum).

[0234] 4. Once the dishware surface is dry the gloss value is measuredagain to determine the change in specular gloss after treatment.

[0235] Analysis:

[0236] 1. Calculate the mean initial (before treatment), and final(after treatment and drying) gloss values for each dishware surface.

[0237] 2. Determine the percent change in specular gloss aftertreatment:$100 \times \frac{\Delta \quad {Gloss}}{{Initial}\quad {Gloss}}$

Count and Measure of Suds and Coating Desirability Effect

[0238] A black 4×12 in. (approximately 10×30 cm) panel obtained from ACTLaboratories, Inc. (Hillsdale, Mich., USA) is washed with 0.2% DAWN®dishwashing liquid in deionized water and rinsed with deionized waterand allowed to air-dry vertically. The rinse aid surface coatingcomposition is sprayed with a Solo Spraystar sprayer on test panel at 5°angle from horizontal and from 6 inches (15 cm) away, once from top tobottom, until panel is thoroughly coated. The sprayer is rinsed with 50mL deionized water between sprayings. A digital picture is then taken ofthe middle 4×4” (10.16×10.16 cm area (referred to as the 100 cm² area)after 30 seconds (timed from completion of spraying). The picture istaken with an Olympus® Camedia D-450ZOOM digital camera mounted on asupport stand with a clamping arm approximately 18 in. (45.7 cm) abovethe panel.

[0239] Suds in the picture are counted using Media Cybemetics® ImagePro®Plus 4.0 software obtained from Media Cybernetics, Inc., 8484 GeorgiaAvenue, Suite 200, Silver Spring Md., 20910, USA. The software is usedto calibrate the image to actual proportions by setting the number ofpixels displaying the width of the panel equal to 10.16 cm. Spatialfiltering tools are then used to enhance the image. Suds are thencounted over the middle 4×4″ area of the panel and each defect ismeasured according to the width of the defect. The size data is thentransferred to a spreadsheet where it can be organized into sizecategories or bins in a histogram.

[0240] Spatial parameters of the image are set using the “Calibration”tool “Spatial” (under “Measure”) by setting the width of the panel equalto 10.16 cm. An area of interest (“AOI”) is then set from the “Edit”menu around the 10.16×10.16 cm area. Background noise is then removedwith filters under the “Spatial Filtering” tab. Under the “Special” tab,“Sculpt” (2 passes at strength 10) filter is used to remove backgroundlighting irregularities and “Erode” filter is used under the“Morphological” tab (2 passes of the “erode” filter at the “3×3 cross”setting) to enhance defects.

[0241] Distribution of bubble sizes is determined with the “Count andMeasure Objects” feature. Under “Measurements to be Taken”, “Size Width”is selected. Under “Options”, “Smoothing” =100, “4 Connect”, and FillHoles are selected. Under “Count/Measure”: “Automatic Dark Objects” isselected. After “Count” is performed, “Data to File” from the “File”menu is selected to transfer the defect size data into a spreadsheet.

[0242] The computer program is essentially “sieving” or categorizing thedefects of various sizes. In the spreadsheet, 13 bins are created forthe histogram. “Defect Size” reports center of range of each bin. Binmaximums (millimeters) are 0.1, 0.25, 0.5, 0.75, 1.0, 1.25, 1.5, 1.75,2.0, 2.5, 5.0, 7.5, and 10.0. The center of each bin range is determinedby the following:$\text{"Defect Size"} = {\frac{\text{bin maximum} - \text{previous bin maximum}}{2} + \text{previous bin maximum.}}$

[0243] The number of defects in the bins of a size greater than equal to1.75 mm is determined.

Visual Grading Test

[0244] Six independent panelists grade the entire panel except for thelower 2 inches of the panel used in the foregoing test for visiblenegatives against an untreated control in a room simulating NorthAmerican light at 12:00 pm (noon). Grading instructions are as follows:

[0245] Purpose: Observers are used to determine the effect ofapplication methods on the desirability of the end result of a coatedsurface.

[0246] Instructions:

[0247] 1. The panelists are instructed to use light to look forirregularities on panel that would draw their attention as a negative.

[0248] 2. Rate desirability of panel appearance against the control (0)on the following scale: 0 = Same −1 = Think it's slightly worse −2 =Know it's a little worse −3 = Definitely worse −4 = Much worse

[0249] 3. The panelists'gradations are then averaged.

Transmittance Test

[0250] Transmittance may be measured using AS™ method D 1003-00.Transmittance may be expressed as a percentage that represents theamount of incident light that passes through the article that may betested.

Viscosity Test

[0251] All measurements are performed with a Brookfield RVDV II+rotational viscometer available from Brookfield Engineering Labs, Inc.,Stoughton, Mass., USA. The recommended procedure may be followed, withthe following exceptions. The recommended procedure may be varied byusing a smaller vessel and removing the guard leg. The calibration maybe determined using a 600 ml low form griffin type beaker with Glycerin(1400 cp) and olive oil (80 cp) at 100 RPM. All subsequent measurementsare performed in 50 ml beakers at 100 RPM with the appropriate spindle.

Optical Profilometry Test

[0252] Optical profilometry has been used to provide a quantitativeestimation of the roughness of the glass surfaces after multi cyclewashes in an automatic dishwasher. Optical profilometry quantifiessurface roughness, step heights, and other topographical features.Profile heights from 0.1 nm up to 5 mm can be measured rapidly andaccurately.

[0253] Optical profilometry employs a beam splinter and a Mirauinterferometer to generate and detect interference patterns in reflectedlight from a sample as a function of surface topography. Maximuminterference contrast is achieved when the sample is in focuds. Thus, tomap surface topography the objective is scanned in the vertical (z)direction through the entire focal plane of the sample. Opticalprofilometry provides quantitative estimation of surface roughness bytwo parameters; height (H: distance from peak to valley) and averageroughness (Ra).

[0254] The disclosure of all patents, patent applications (and anypatents which issue thereon, as well as any corresponding publishedforeign patent applications), and publications mentioned throughout thisdescription are hereby incorporated by reference herein. It is expresslynot admitted, however, that any of the documents incorporated byreference herein teach or disclose the present invention.

[0255] While particular embodiments of the subject invention have beendescribed, it will be obvious to those skilled in the art that variouschanges and modifications of the subject invention can be made withoutdeparting from the spirit and scope of the invention. It may be intendedto cover, in the appended claims, all such modifications that may bewithin the scope of the invention.

EXAMPLE(S)

[0256] The following provides several non-limiting examples of thepresent invention. In the experiments described in the followingexamples, dishware articles stained with a standard evaluation stainwere used to evaluate coating and spot formation. The experiments wereconducted in a number of commercially available automatic dishwashingappliances. In the automatic dishwashing experiments, the automaticdishwashing appliance was operated at the appropriate temperature withthe water hardness adjusted. Commercially available appliance automaticdishwashing detergent (powder, tablet and liquid gel) was added. Theneither a rinse aid with nanoclay, a rinse aid without nanoclay or acommercially available rinse aid was added to the rinse cycle at adosage of 2-3 mL per rinse for direct comparison.

[0257] Dishware articles, when dry, were examined by image analysis forcoating and spot formation, using the following 1-10 scale: 1=worstcoating/spot grade; 10=best (no coating, no spot).

Nanoclay Coating/Spot Behavior Example 1

[0258] In Example 1, the coating and spot formation effects of nanoclay(LAPONITE RD™) as a rinse aid on a standard set of glasses weredetermined at various concentrations of LAPONITE RD™ relative to nonanoclay or no commercially available rinse aid in the rinse cycle.Results are shown in Table 1. This experiment was conducted in acommercially available General Electric automatic dishwasher, GE 500,using Cascade powder detergent in the main wash at a concentration 7.1g/L. The wash temperature was 55° C. and water hardness was adjusted to3.3 mM (Calcium:Magnesium=3:1). TABLE 1 Treatment Filming Grade SpottingGrade No rinse aid 4.9 7.9 25 ppm LAPONITE¹ RD ™ 8.7 7.6 100 ppmLAPONITE RD ™ 10 8.7 500 ppm LAPONITE RD ™ 10 8.4

Structural Variation of Nanoclay on Coating/Spot Formation Example 2

[0259] The effect of structural variation of nanoclay (LAPONITE RD™versus LAPONITE B™) as a rinse aid on the spot and coating formation wasinvestigated on a standard set of glasses. The experiment was conductedin a GE 500 appliance at 55° C. wash temperature and water hardness of3.3 mM (calcium:magnesium=3:1). Cascade powder was used as a washdetergent of 7.1 g/L concentration. In this experiment, the effect ofconcentration of LAPONITE B™ on the spot, coating formation behavior wasalso examined. The results are shown in Table 2 TABLE 2 Spot TreatmentCoating Grade, 1^(st) cycle Grade, 1^(st) cycle No rinse aid 4.4 7.8LAPONITE RD ™, 25 ppm 7.3 7.1 LAPONITE B ™, 25 ppm 8.3 7.5 LAPONITE B ™,10 ppm 8.0 7.7

Effect of Polyacrylate on Coating Formation of Nanoclay Example 3

[0260] The influence of dispersant polymer (polyacrylate, MW 4500) onthe coating formation behavior of nanoclay (LAPONITE B™) on a set ofstandard glasses in a single- and multi-cycle rinse relative to acommercially available rinse aid was assessed. The experiment wasperformed in a GE 500 appliance using cascade powder in the main wash(7.1 g/L) at a temperature of 55° C. and 2.0 mM water hardness(Ca:Mg=3:1) hardness. The result of this experiment is shown in Table 3.TABLE 3 Coating Grade Treatment 1^(st) Cycle 4^(th) Cycle Commercialrinse aid (280 ppm) 5.8 6.7 LAPONITE B ™ (25 ppm) 7.5 8.4 LAPONITE B ™(25 ppm) + Polyacrylate¹ (5 9.5 8.4 ppm)

Effect of Polyacrylate on Spot Formation of Nanoclay Example 4

[0261] The effect of dispersant polymer (polyacrylate) on the spotformation behavior of nanoclay (LAPONITE B™) on glasses in a single- andmulti-cycle rinse cycle was evaluated in an identical experimentalcondition as described in Example 3. The result of this experiment isshown in Table 4. TABLE 4 Spot Grade Treatment 1^(st) Cycle 4^(th) CycleCommercial rinse aid (280 ppm) 9.0 8.9 LAPONITE B ™ (25 ppm) 7.9 7.9LAPONITE B ™ (25 ppm) + Polyacrylate, 5 8.3 8.3 ppm

Nanoclay Multi-Cycle Coating Benefit Example 5

[0262] The single and multi-cycle coating formation behavior of nanoclay(LAPONITE B™) in combination with polyacrylate as a rinse aid on glassand stainless steel dishware articles was evaluated in a commerciallyavailable European Bosch appliance. A commercially available automaticdishwashing detergent tablet was used in the main wash. London Citywater of 3.3Mm water hardness (Ca:Mg=3:1) and a wash temperature of 65°C., 50 g stain was used in this experiment. Results are shown in Table5. TABLE 5 Glass S/S Spatula Cycle Cycle Cycle Cycle Cycle Treatment 1 5Cycle 10 1 5 10 Commercial rinse aid 8.9 8.7 4.1 10 10 10 LAPONITE B ™8.7 8.5 8.4 10 10 10 (10 ppm) + Polyacrylate (2 ppm)

Nanoclay Multi-Cycle Spot Benefit Example 6

[0263] The single and multi-cycle spot formation behavior of nanoclay(LAPONITE B™) in combination with polyacrylate as a rinse aid on glassand stainless spatula was evaluated in an identical experimentalcondition as described in Example 5. Results are shown in Table 6. TABLE6 Glass S/S Spatula Cycle Cycle Cycle Cycle Cycle Treatment 1 5 Cycle 101 5 10 Commercial rinse aid 5.9 5.5 3.4 8 8 8 LAPONITE B ™ 5.7 5.3 4.5 88 8 (10 ppm) + Polyacrylate (2 ppm)

Rinse Aid surface coating Grade Example 7

[0264] The coating formation property of nanoclay (LAPONITE B™) incombination with polyacrylate and acrylic acid/maleic acid copolymerrelative to a commercially available rinse aid across a broad range ofdish articles were investigated in the rinse cycle in a GE 500appliance. A commercially available automatic dishwasher liquid gelproduct at a concentration 8.0 g/L was used in the main wash using awash temperature of 55° C. and 2.7 mM artificial hardness (Ca:Mg =3:1)with standard stain loads. Results are shown in Table 7. TABLE 7Treatment Glass Plastic Stoneware Stainless Commercial rinse aid 4.3 3.67.4 6.2 LAPONITE B ™ (15 ppm) + 6.8 4.5 9.4 7.9 Polyacrylate¹ (1.5ppm) + Alcrylic acid/Maleic acid copolymer (1.5 ppm)

Spot Grade Example 8

[0265] Spot formation behavior of nanoclay (LAPONITE B™) in the presencepolyacrylate, acrylic acid, maleic acid copolymer relative to acommercially available rinse aid was examined in the rinse cycle.Experimental conditions of this experiment were identical to the onedescribed in Example 7. Results are shown in Table 8. TABLE 8 TreatmentGlass Plastic Stone ware Stainless Cascade gel + Emerald 8.7 2.5 9.910.0 Rinse Aid Cascade gel + 5% 7.7 5.3 9.0  9.9 LAPONITE B ™ (15 ppm) +Polyacrylate (3 ppm)

Examples 9-16

[0266] Liquid rinse aid surface coating compositions, according to thepresent invention, where the balance may be water, and where saidsurface coating composition can be applied to a surface, or optionallywhere the rinse aid surface coating composition can be diluted withwater to achieve a rinse aid surface coating composition with 0.1%concentration of nanoparticles are as follows: TABLE 9 Ex- am- ple #Nanoparticle (Wt %) Surfactant (Wt %) Dispersant (Wt %)  9 Nanoclay(1.6) Q2-5211 (0.8) None 10 Nanoclay (0.8) Q2-5211 (0.4) None 11Nanoclay (0.8) Neodol 91-6 (0.6) None 12 Disperal P2 ™ (10) Neodol 91-6(7.5) None 13 Nanoclay (5.0) Neodol⁴ 91-6 (3.75) Polyacrylate 4500³ MW(1.0) 14 Nanoclay (5.0) Neodol 91-6 (3.75) Poly (acrylic/ maleic) acidCopolymer¹ (1.0) 15 Nanoclay (1.0) Neodol 91-6 (0.75) Polyacrylate 4500³MW (0.2) 16 Nanoclay (1.0) Neodol 91-6 (0.75) Polyacrylate 4500 MW (0.1)

Examples 17-19

[0267] Granular, rinse aid surface coating compositions for dishware,according to the present invention, which can be placed into the rinseaid cup of a dishwasher and dispensed through the rinse cycle forimproved spotting filming benefits on dishware surfaces are as follows:TABLE 10 Component % by weight Examples 17 18 19 1. Plurafac RA30 35 — —2. Citric Acid 3 — — 3. Acusol 480 8 — — 4. Naxonate 45SC 9 — — 5. DTPMP0.05 — — 6. Nanoclay 0.005-2 0.005-2 0.005-2 7. Ether capped — —  0.01-1poly(oxyalkylated) alcohol 8. Ethanol 7 — — 9. Perfume 0.1 — — 10. Dye0.3 — — 11. Water Balance Balance Balance

[0268] 7. Ether capped poly(oxyalkylated) alcohol acts as a nonionicwetting agent.

[0269] 8. Ethanol is used for viscosity control.

[0270] 9. Perfume and Dyes are optional.

Examples 20 and 21

[0271] Liquid rinse aid surface coating compositions for dishware,according to the present invention, which can be placed in a spraybottled and delivered as a spray-on formula for improved tough foodstain release benefits on dishware surfaces are as follows: TABLE 11Component % by weight Examples 20 21 1. Nanoclay 0.005-2 0.005-2 2.Ether capped poly(oxyalkylated) alcohol —  0.01-1 3. Water BalanceBalance

Care Benefit of LAPONITE™ Examples 22 and 23

[0272] LAPONITE B™ provides care benefits on a broad based of disharticle substrates (glass, china, metal). Experiments were conducted insoft water through 100 wash cycles. In this study, dish articles werewashed with commercial detergents in the main wash, commercial rinse aidand LAPONITE™ was added in the rinse cycles separately for directcomparison. Optical profilometry provides quantitative estimation ofsurface roughness by two parameters; height (H: distance from peak tovalley) and average roughness (Ra). Both these parameters as indicatedin the following examples in Table 12 and show that LAPONITE B™ treatedglass surfaces are less rough than the commercially available rinse aidtreated surfaces. TABLE 12 China Glass Treatment H (nm) Ra (nm) H (nm)Ra (nm) Examples 22 23 Untreated (new surface) 90.0 24.3 14.9 4.8Commercial Rinse aid (280 ppm) 131.3 37.8 23.8 5.6 LAPONITE B ™ (25 ppm)91.5 25.0 12.4 3.7

[0273] The above coating compositions when applied to a dishwaresurface, modify the dishware surface to exhibit at least one of thefollowing multi-use benefits consisting of improved dishware surface:wetting and sheeting, uniform drying, anti-spotting, anti-staining,anti-filming, self cleaning, and durability; as compared to a dishwaresurface not treated with said rinse aid surface coating composition.

[0274] In the case of any of the embodiments described in this detaileddescription, unless specified otherwise, the coating can be applied tothe dishware surface with or without the active curing step. It may beunderstood that the active curing step is useful because it is believedto provide the coating with additional durability. The coatingsdescribed herein can be applied at any suitable time in the life of thedishware surface including during or after manufacture of the dishwaresurface, if it is a type of dishware surface that is manufactured. Thecoating can also be applied during the life of the dishware surface forprotective purposes, preventative purposes, or any other purposes.

[0275] While particular embodiments of the subject invention have beendescribed, it will be obvious to those skilled in the art that variouschanges and modifications of the subject invention can be made withoutdeparting from the spirit and scope of the invention. It may be intendedto cover, in the appended claims, all such modifications that are withinthe scope of the invention.

What is claimed is:
 1. A rinse aid surface coating composition for atleast partially covering a dishware surface, said surface coatingcomposition comprising: a) a plurality of nonphotoactive nanoparticleswhich are present in an amount less than about 3 mg/cm² of the area ofdishware surface; b) a carrier, at least some of which is aqueous; c)optionally a dispersant polymer; d) optionally a surfactant; e)optionally a wetting agent; f) optionally a pH-adjusting agent; and g)less than about 10% by weight of other ingredients; wherein said surfacecoating composition is non-thixotropic; and wherein at lease some ofsaid nanoparticles comprise a synthetic mineral selected from the groupconsisting of hectorite, fluorohectorite, and mixtures thereof.
 2. Thesurface coating composition according to claim 1 wherein saidnanoparticles are present in an amount less than about 3 μg/cm² of thearea of dishware surface.
 3. The surface coating composition accordingto claim 1 wherein the wherein said nanoparticles consist essentially ofhectorite, fluorohectorite, and mixtures thereof.
 4. The surface coatingaccording to claim 1 wherein at least some of said nanoparticlescomprise smectite.
 5. The surface coating composition according to claim1 wherein at least about one half of said nanoparticles comprisehectorite.
 6. The surface coating composition according to claim 1wherein at least about one half of said nanoparticles comprisefluorohectorite.
 7. The surface coating composition according to claim 1wherein said surface coating composition further comprises a dispersantpolymer selected from the group consisting of polyacrylic acid, poly(acrylic/allyl alcohol), poly (acrylic/maleic), polycarboxylic acids,sodium tripolyphosphate, pyrophosphate, and mixtures thereof.
 8. Thesurface coating composition according to claim 7 wherein said dispersantpolymer is selected from the group consisting of polyacrylates, acrylicacid/maleic acid copolymers, and mixtures thereof.
 9. The surfacecoating composition according to claim 1 wherein said surface coatingcomposition further comprises a surfactant selected from the groupconsisting of anionic surfactants, cationic surfactants, nonionicsurfactants, amphoteric surfactants, ampholytic surfactants,zwitterionic surfactants, and mixtures thereof.
 10. The surface coatingcomposition according to claim 9 wherein said surfactant is alow-foaming nonionic surfactant with a cloud point below about 30° C.11. The surface coating composition according to claim 10 wherein saidlow-foaming nonionic surfactant is selected from the group consisting ofC_(9/11)EO₈-cyclohexyl acetal alkyl capped nonionic, C₁₁E₇-n-butylacetal, C_(9/11) E₈-2-ethylhexyl acetal, C₁ ₁E0₈-pyranyl, alcoholalkoxylate, and mixtures thereof.
 12. The surface coating compositionaccording to claim 11 wherein said low foaming surfactant has a cloudpoint below about 20° C.
 13. The surface coating composition accordingto claim 1 further comprising at least one wetting agent.
 14. Thesurface coating composition according to claim 1 further comprising atleast one pH-adjusting agent.
 15. The surface coating compositionaccording to claim 1 containing less than 3% peptizer.
 16. The surfacecoating composition according to claim 1 wherein said other ingredientscomprise adjunct materials are selected from the group consisting ofinorganic metal oxides, organic solvents, surfactants, polymers,builders, bleaches, bleach activators, bleach catalysts, non-activatedenzymes, enzyme stabilizing systems, chelants, optical brighteners,stain release polymers, dye transfer agents, suds suppressors, dyes,perfumes, colorants, filler salts, hydrotropes, fluorescers,conditioners, hydrolyzable cosurfactants, perservatives, anti-oxidants,anti-shrinkage agents, germicides, fungicides, color speckles,silvercare, anti-tamish and/or anti-corrosion agents, alkalinitysources, solubilizing agents, carriers, processing aids, pigments, andmixtures thereof.
 17. The surface coating composition according to claim1 consisting essentially of nanoparticles, a dispersant, a surfactant, awetting agent, a pH-adjusting agent and water; wherein saidnanoparticles comprise a synthetic mineral selected from the groupconsisting of hectorite, fluorohectorite, and mixtures thereof.
 18. Thesurface coating according to claim 1 having an exposed first surface anda second surface adjacent the surface to which it is applied, whereinsaid first surface of said surface coating is hydrophilic.
 19. Thesurface coating according to claim 1 which is less than 300 nanometersthick.
 20. The surface coating according to claim 1 which istransparent.
 21. The surface coating according to claim 1 which issubstantially continuous.
 22. A method of forming a surface coating forat least partially covering a dishware surface, said method comprising:a) locating a substrate with a dishware surface; b) depositing anaqueous rinse aid surface coating composition according to claim 1 onsaid dishware surface of said substrate, said non-photoactivenanoparticles being deposited in an amount less than 3 μg/cm² of thearea of the surface; and c) allowing said composition to dry withoutfurther rinsing or agitating the same so that a substantially clear,hydrophilic coating is formed on said surface.
 23. The method accordingto claim 22 wherein said surface coating is less than 300 nanometersthick.
 24. The method according to claim 22 wherein said surface coatingcomposition is deposited by spraying the composition onto the dishwaresurface during the wash and/or rinse cycle of an automatic dishwashingappliance.
 25. The method according to claim 22 wherein said surfacecoating composition is sprayed onto the dishware surface by anelectrostatic sprayer.
 26. The method according to claim 22 wherein thestep (b) of depositing said surface coating composition on the dishwaresurface forms a wet surface coating on said dishware surface.
 27. Themethod according to claim 22 wherein said wet surface coating has lessthan 60 defects of a size greater than or equal to 1.75 mm per 100 cm²of the dishware surface as measured at any time more than 30 secondsafter the wet surface coating is formed on said dishware surface. 28.The method according to claim 22 wherein said at least some of saidnanoparticles are disc-shaped or platelet-shaped, and said disc-shapedor platelet-shaped nanoparticles have at least one dimension that isgreater than or equal to about 0.5 nanometers, and an aspect ratio isgreater than or equal to about
 15. 29. The method according to claim 22wherein said at least some of said nanoparticles are rod-shaped, andsaid rod-shaped nanoparticles have at least one dimension that isgreater than or equal to about 0.5 nanometers, and an aspect ratio isgreater than or equal to about
 3. 30. The method according to claim 22wherein when said surface coating at least partially covers a dishwaresurface that has an initial specular gloss reading before said surfacecoating composition is applied of greater than or equal to 10 at 60°geometry, said dishware surface with said surface coating thereon hasless than or equal to a 10% reduction in specular gloss value whenmeasured at the geometry specified in the Specular Gloss test.
 31. Themethod according to claim 22 wherein when said surface coating at leastpartially covers a dishware surface that has an initial specular glossreading before said surface coating composition is applied of less than10 at 60° geometry, said dishware surface with said coating thereon hasan increase of greater than or equal to a 10% in specular gloss valuewhen measured at the geometry specified in the Specular Gloss test. 32.The method according to claim 22 wherein the visual dry surface coatingscore is greater than or equal to (−2).